Insecticidal compounds

ABSTRACT

The invention relates to compounds of formula (I): 
     
       
         
         
             
             
         
       
     
     where A 1 , A 2 , A 3 , A 4 , G, R 1 , R 2 , R 3  and R 4  are as defined in claim  1 ; or a salt or N-oxide thereof. 
     Furthermore, the present invention relates to processes and intermediates for preparing compounds of formula (I), to insecticidal, acaricidal, nematicidal and molluscicidal compositions comprising the compounds of formula (I) and to methods of using the compounds of formula (I) to control insect, acarine, nematode and mollusc pests.

This application is a continuation of U.S. patent application Ser. No.13/379,812, filed Mar. 14, 2012, which was a national phase ofInternational Application No. PCT/EP2010/058207, filed Jun. 11, 2010,which claims priority to GB 0910768.1 filed Jun. 22, 2009, GB 0910767.3filed Jun. 22, 2009, PCT/EP2009/059563 filed Jul. 24, 2009, and EP10153810.6 filed Feb. 17, 2010, the contents of which are incorporatedherein by reference.

The present invention relates to certain dihydro-pyrrole derivativeswith a four-membered ring as terminal group, to processes andintermediates for preparing these derivatives, to insecticidal,acaricidal, nematicidal and molluscicidal compositions comprising thesederivatives and to methods of using these derivatives to control insect,acarine, nematode and mollusc pests.

Certain dihydro-pyrrole derivatives with insecticidal properties aredisclosed in, for example, JP 2007/091708 and JP 2008/133273.

It has now surprisingly been found that dihydro-pyrrole derivatives witha four-membered ring as terminal group have insecticidal properties.

The present invention therefore provides a compound of formula (I)

whereA¹, A², A³ and A⁴ are independently of each other C—H, C—R⁵ or nitrogen;G is oxygen or sulfur;R¹ is hydrogen, C₁-C₈alkyl, C₁-C₈alkoxy-, C₁-C₈alkylcarbonyl- orC₁-C₈alkoxycarbonyl-;R² is a group of formula (II)

whereL is a single bond or C₁-C₆alkylene; andY¹, Y² and Y³ are independently of another CR⁸R⁹, C═O, C═N—OR¹⁰, N—R¹⁰,S, SO, SO₂, S═N—R¹⁰ or SO═N—R¹⁰, provided that at least one of Y¹, Y² orY³ is not CR⁸R⁹, C═O or C═N—OR¹⁰;R³ is C₁-C₈haloalkyl;R⁴ is aryl or aryl substituted by one to five R⁷, or heteroaryl orheteroaryl substituted by one to five R⁷;each R⁵ is independently halogen, cyano, nitro, C₁-C₈alkyl,C₁-C₈haloalkyl, C₁-C₈alkenyl, C₁-C₈haloalkenyl, C₁-C₈alkynyl,C₁-C₈haloalkynyl, C₃-C₁₀cycloalkyl, C₁-C₈alkoxy-, C₁-C₈haloalkoxy-,C₁-C₈alkylthio-, C₁-C₈haloalkylthio-, C₁-C₈alkylsulfinyl-,C₁-C₈haloalkylsulfinyl-, C₁-C₈alkylsulfonyl- or C₁-C₈haloalkylsulfonyl-,ortwo R⁵ on adjacent carbon atoms together form a —CH═CH—CH═CH— bridge;R⁶ is hydrogen or C₁-C₈alkyl;each R⁷ is independently halogen, cyano, nitro, C₁-C₈alkyl,C₁-C₈haloalkyl, C₂-C₈alkenyl, C₂-C₈haloalkenyl, C₂-C₈alkynyl,C₂-C₈haloalkynyl, hydroxy, C₁-C₈alkoxy-, C₁-C₈haloalkoxy-, mercapto,C₁-C₈alkylthio-, C₁-C₈haloalkylthio-, C₁-C₈alkylsulfinyl-,C₁-C₈haloalkylsulfinyl-, C₁-C₈alkylsulfonyl-, C₁-C₈haloalkylsulfonyl-,C₁-C₈alkylcarbonyl-, C₁-C₈alkoxycarbonyl-, aryl or aryl substituted byone to five R¹¹, or heterocyclyl or heterocyclyl substituted by one tofive R¹¹;each R⁸ and R⁹ is independently hydrogen, halogen, C₁-C₈alkyl orC₁-C₈haloalkyl;each R¹⁰ is independently hydrogen, cyano, C₁-C₈alkyl, C₁-C₈haloalkyl,C₁-C₈alkylcarbonyl-, C₁-C₈haloalkylcarbonyl-, C₁-C₈alkoxycarbonyl-,C₁-C₈haloalkoxycarbonyl-, C₁-C₈alkylsulfonyl-, C₁-C₈haloalkylsulfonyl-,aryl-C₁-C₄alkylene- or aryl-C₁-C₄alkylene- where the aryl moiety issubstituted by one to three R¹², or heteroaryl-C₁-C₄alkylene- orheteroaryl-C₁-C₄alkylene- where the heteroaryl moiety is substituted byone to three R¹²;each R¹¹ and R¹² is independently halogen, cyano, nitro, C₁-C₈alkyl,C₁-C₈haloalkyl, C₁-C₈alkoxy-, C₁-C₈haloalkoxy- or C₁-C₈alkoxycarbonyl-;or a salt or N-oxide thereof.

The compounds of formula (I) may exist in different geometric or opticalisomers or tautomeric forms. This invention covers all such isomers andtautomers and mixtures thereof in all proportions as well as isotopicforms such as deuterated compounds.

The compounds of the invention may contain one or more asymmetric carbonatoms, for example, at the —CR³R⁴— group, and may exist as enantiomers(or as pairs of diastereoisomers) or as mixtures of such.

Alkyl groups (either alone or as part of a larger group, such asalkoxy-, alkylthio-, alkylsulfinyl-, alkylsulfonyl-, alkylcarbonyl- oralkoxycarbonyl-) can be in the form of a straight or branched chain andare, for example, methyl, ethyl, propyl, prop-2-yl, butyl, but-2-yl,2-methyl-prop-1-yl or 2-methyl-prop-2-yl. The alkyl groups are, unlessindicated to the contrary, preferably C₁-C₆, more preferably C₁-C₄, mostpreferably C₁-C₃ alkyl groups.

Alkylene groups can be in the form of a straight or branched chain andare, for example, —CH₂—, —CH₂—CH₂—, —CH(CH₃)—, —CH₂—CH₂—CH₂—,—CH(CH₃)—CH₂—, or —CH(CH₂CH₃)—. The alkylene groups are, unlessindicated to the contrary, preferably C₁-C₃, more preferably C₁-C₂, mostpreferably C₁ alkylene groups.

Alkenyl groups can be in the form of straight or branched chains, andcan be, where appropriate, of either the (E)- or (Z)-configuration.Examples are vinyl and allyl. The alkenyl groups are, unless indicatedto the contrary, preferably C₂-C₆, more preferably C₂-C₄, mostpreferably C₂-C₃ alkenyl groups.

Alkynyl groups can be in the form of straight or branched chains.Examples are ethynyl and propargyl. The alkynyl groups are, unlessindicated to the contrary, preferably C₂-C₆, more preferably C₂-C₄, mostpreferably C₂-C₃ alkynyl groups.

Halogen is fluorine, chlorine, bromine or iodine.

Haloalkyl groups (either alone or as part of a larger group, such ashaloalkoxy-, haloalkylthio-, haloalkylsulfinyl-, haloalkylsulfonyl-,haloalkylcarbonyl- or haloalkoxycarbonyl-) are alkyl groups which aresubstituted by one or more of the same or different halogen atoms andare, for example, difluoromethyl, trifluoromethyl, chlorodifluoromethylor 2,2,2-trifluoro-ethyl.

Haloalkenyl groups are alkenyl groups which are substituted by one ormore of the same or different halogen atoms and are, for example,2,2-difluoro-vinyl or 1,2-dichloro-2-fluoro-vinyl.

Haloalkynyl groups are alkynyl groups which are substituted by one ormore of the same or different halogen atoms and are, for example,1-chloro-prop-2-ynyl.

Cycloalkyl groups can be in mono- or bi-cyclic form and are, forexample, cyclopropyl, cyclobutyl, cyclohexyl andbicyclo[2.2.1]heptan-2-yl. The cycloalkyl groups are, unless indicatedto the contrary, preferably C₃-C₈, more preferably C₃-C₆ cycloalkylgroups.

Aryl groups are aromatic ring systems which can be in mono-, bi- ortricyclic form. Examples of such rings include phenyl, naphthyl,anthracenyl, indenyl or phenanthrenyl. Preferred aryl groups are phenyland naphthyl, phenyl being most preferred. Where an aryl moiety is saidto be substituted, the aryl moiety is, unless indicated to the contrary,preferably substituted by one to four substituents, most preferably byone to three substituents.

Heteroaryl groups are aromatic ring system containing at least oneheteroatom and consisting either of a single ring or of two or morefused rings. Preferably, single rings will contain up to threeheteroatoms and bicyclic systems up to four heteroatoms which willpreferably be chosen from nitrogen, oxygen and sulfur. Examples ofmonocyclic groups include pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl,pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furanyl, thiophenyl,oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl andthiadiazolyl. Examples of bicyclic groups include quinolinyl,cinnolinyl, quinoxalinyl, indolyl, indazolyl, benzimidazolyl,benzothiophenyl and benzothiazolyl. Monocyclic heteroaryl groups arepreferred, pyridyl being most preferred. Where a heteroaryl moiety issaid to be substituted, the heteroaryl moiety is, unless indicated tothe contrary, preferably substituted by one to four substituents, mostpreferably by one to three substituents.

Heterocyclyl groups are defined to include heteroaryl groups and inaddition their unsaturated or partially unsaturated analogues. Examplesof monocyclic groups include thietanyl, pyrrolidinyl, tetrahydrofuranyl,[1,3]dioxolanyl, piperidinyl, piperazinyl, [1,4]dioxanyl, andmorpholinyl or their oxidised versions such as 1-oxo-thietanyl and1,1-dioxo-thietanyl. Examples of bicyclic groups include2,3-dihydro-benzofuranyl, benzo[1,3]dioxolanyl, and2,3-dihydro-benzo[1,4]dioxinyl. Where a heterocyclyl moiety is said tobe substituted, the heterocyclyl moiety is, unless indicated to thecontrary, preferably substituted by one to four substituents, mostpreferably by one to three substituents.

Preferred values of A¹, A², A³, A⁴, G, R¹, R², R³, R⁴, L, Y¹, Y², Y³,R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³ and m are, in any combination, asset out below.

Preferably no more than two of A¹, A², A³ and A⁴ are nitrogen.

Preferably A¹ is C—H or C—R⁵, most preferably A¹ is C—R⁵.

Preferably A² is C—H or C—R⁵, most preferably A² is C—H.

Preferably A³ is C—H or C—R⁵, most preferably A³ is C—H.

Preferably A⁴ is C—H or C—R⁵, most preferably A⁴ is C—H.

In one preferred group of compounds A¹, A², A³ and A⁴ are independentlyof each other C—H or C—R⁵.

In one preferred group of compounds A¹ is C—R⁵, A² is C—H, A³ is C—H ornitrogen and A⁴ is C—H or nitrogen.

In another preferred group of compounds A¹ is C—R⁵, A² is C—H, A³ is C—Hor nitrogen and A⁴ is C—H.

In a further preferred group of compounds A¹ is C—R⁵, A² is C—H, A³ isC—H and A⁴ is C—H.

Preferably G is oxygen.

Preferably R¹ is hydrogen, methyl, ethyl, methylcarbonyl- ormethoxycarbonyl-, more preferably hydrogen, methyl or ethyl, mostpreferably hydrogen.

Preferably R² is a group of formula (IIa)

whereL is a single bond, methylene, ethylene or propylene,R¹³ is C₁-C₈alkyl,m is 0, 1, 2, 3, 4, or 5, andone of Y¹ and Y² is S, SO, SO₂, S═N—R¹⁰, SO═N—R¹⁰ or C═N—OR¹⁰, e.g. S,SO, SO₂, S═N—R¹⁰ or SO═N—R¹⁰, e.g. S, SO, SO₂ or C═N—OR¹⁰, e.g. S, SO orSO₂, and the other is CH₂ in which each H may be replaced by R¹³.

More preferably R² is a group of formula (IIb)

whereL is a single bond, methylene, ethylene or propylene,R¹³ is hydrogen or C₁-C₈alkyl, e.g. C₁-C₈alkyl, andone of Y¹ and Y² is S, SO, SO₂, S═N—R¹⁰, SO═N—R¹⁰ or C═N—OR¹⁰, e.g. S,SO, SO₂, S═N—R¹⁰ or SO═N—R¹⁰, e.g. S, SO, SO₂ or C═N—OR¹⁰, e.g. S, SO orSO₂, and the other is CH₂.

More preferably R² is a group of formula (IIc)

whereR¹³ is C₁-C₈alkyl, preferably methyl,m is 0, 1, 2, 3, 4, or 5, andY² is S, SO, SO₂, S═N—R¹⁰, SO═N—R¹⁰ or C═N—OR¹⁰, e.g. S, SO, SO₂ orC═N—OR¹⁰, e.g. S, SO or SO₂.

Even more preferably R² is a group of formula (IId)

whereR¹³ is hydrogen or C₁-C₈alkyl, e.g. C₁-C₈alkyl, e.g. hydrogen or methyl,andY² is S, SO, SO₂, S═N—R¹⁰, SO═N—R¹⁰ or C═N—OR¹⁰, e.g. S, SO, SO₂ orC═N—OR¹⁰, e.g. S, SO or SO₂,

Most preferably R² is thietan-3-yl-, 1-oxo-thietan-3-yl-,1,1-dioxo-thietan-3-yl- or 3-methyl-thietan-3-yl-.

In another preferred group of compounds R² is a group of formula (IIc′)

whereR¹³ is C₁-C₈alkyl,m is 0, 1, 2, 3, 4, or 5, and

Y² is S, SO, SO₂, S═N—R¹⁰ or SO═N—R¹⁰.

In another group of preferred compounds R² is a group of formula (IId′)

whereR¹³ is C₁-C₈alkyl, and

Y² is S, SO, SO₂, S═N—R¹⁰ or SO═N—R¹⁰.

Preferably R³ is chlorodifluoromethyl or trifluoromethyl, mostpreferably trifluoromethyl.

Preferably R⁴ is phenyl or phenyl substituted by one to five R⁷, morepreferably phenyl substituted by one to three R⁷, even more preferablyR⁴ is 3,5-dibromo-phenyl-, 3,5-dichloro-phenyl-,3,5-bis-(trifluoromethyl)-phenyl-, 3,4-dichloro-phenyl-,3,4,5-trichloro-phenyl- or 3-trifluoromethyl-phenyl-, most preferably3,5-dichloro-phenyl.

Preferably L is a single bond, methylene, ethylene or propylene.

More preferably L is methylene or a single bond.

Even more preferably L is a single bond.

Preferably Y¹ is CR⁸R⁹, more preferably CH₂.

Preferably Y² is S, SO, SO₂, S═N—R¹⁰, SO═N—R¹⁰, or C═N—OR¹⁰, e.g. S, SO,SO₂, S═N—R¹⁰ or SO═N—R¹⁰, more preferably S, SO, SO₂, S═N—C≡N, SO═NH,SO═N—C≡N or C═N—OR¹⁰ e.g. S, SO, SO₂, S═N—C≡N, SO═NH or SO═N—C≡N, mostpreferably S, SO, SO₂ or C═N—OR¹⁰, e.g. S, SO or SO₂.

Preferably Y³ is CR⁸R⁹, more preferably CH₂.

Preferably each R⁵ is independently halogen, C₁-C₈alkyl, C₁-C₈haloalkylor C₁-C₈alkenyl, or two R⁵ on adjacent carbon atoms together form a—CH═CH—CH═CH— bridge, more preferably each R⁵ is independently bromo,chloro, fluoro, methyl, trifluoromethyl or vinyl, or two R⁵ on adjacentcarbon atoms, preferably R⁵ on A¹ and A², together form a —CH═CH—CH═CH—bridge, most preferably each R⁵ is independently methyl.

Preferably R⁶ is methyl or hydrogen.

Preferably each R⁷ is independently halogen, cyano, C₁-C₈alkyl,C₁-C₈haloalkyl or C₁-C₈alkoxy-, more preferably bromo, chloro, fluoro,cyano, methyl, trifluoromethyl, methoxy or trifluoromethoxy, preferablybromo, chloro or trifluoromethyl, most preferably bromo or chloro.

Preferably each R⁸ is independently hydrogen or C₁-C₈alkyl, morepreferably hydrogen or methyl, most preferably hydrogen.

Preferably each R⁹ is independently hydrogen or C₁-C₈alkyl, morepreferably hydrogen or methyl, most preferably hydrogen.

Preferably each R¹⁰ is independently methyl, hydrogen or cyano, e.g.hydrogen or cyano, preferably methyl or hydrogen, e.g. hydrogen.

Preferably each R¹¹ is independently bromo, chloro, fluoro, cyano,nitro, methyl, ethyl, trifluoromethyl, methoxy, difluoromethoxy ortrifluoromethoxy, more preferably bromo, chloro, fluoro, nitro ormethyl, most preferably chloro, fluoro or methyl.

Preferably each R¹² is independently bromo, chloro, fluoro, cyano,nitro, methyl, ethyl, trifluoromethyl, methoxy, difluoromethoxy ortrifluoromethoxy, more preferably bromo, chloro, fluoro, nitro ormethyl, most preferably chloro, fluoro or methyl.

Preferably each R¹³ is independently methyl.

Preferably m is 0 or 1, most preferably 0.

A group of preferred compounds are those wherein A¹, A², A³ and A⁴ areindependently of each other C—H or C—R⁵, preferably A¹ is C—R⁵, A² isC—H, A³ is C—H or nitrogen and A⁴ is C—H or nitrogen;

G is oxygen;

R¹ is hydrogen, methyl, ethyl, methylcarbonyl- or methoxycarbonyl-;

R² is a group of formula (IIa)

where

L is a single bond, methylene methylene, ethylene or propylene,

m is 0, 1, 2, 3, 4, or 5, and

one of Y¹ and Y² is S, SO, SO₂, S═N—R¹⁰, SO═N—R¹⁰ or C═N—OR¹⁰, and theother is CH₂ in which each H may be replaced by R¹³.

R³ is C₁-C₈ haloalkyl;

R⁴ is phenyl substituted by one to three R⁷;

each R⁵ is independently halogen, C₁-C₈alkyl, C₁-C₈haloalkyl orC₁-C₈alkenyl, or two R⁵ on adjacent carbon atoms together form a—CH═CH—CH═CH— bridge;

each R⁷ is independently halogen, cyano, C₁-C₈alkyl, C₁-C₈haloalkyl orC₁-C₈alkoxy-;

each R¹⁰ is independently methyl, hydrogen or cyano;

R¹³ is C₁-C₈alkyl,

Another group of preferred compounds are those wherein

A¹, A², A³ and A⁴ are independently of each other C—H or C—R⁵,preferably A¹ is C—R⁵, A² is C—H, A³ is C—H and A⁴ is C—H;

G is oxygen;

R¹ is hydrogen, methyl or ethyl;

R² is a group of formula (IIb)

where

L is a single bond methylene, ethylene or propylene,

one of Y¹ and Y² is S, SO, SO₂, S═N—R¹⁰, SO═N—R¹⁰ or C═N—OR¹⁰ and theother is CH₂;

R³ is chlorodifluoromethyl or trifluoromethyl;

R⁴ is 3,5-dibromo-phenyl-, 3,5-dichloro-phenyl-,3,5-bis-(trifluoromethyl)-phenyl-, 3,4-dichloro-phenyl-,3,4,5-trichloro-phenyl- or 3-trifluoromethyl-phenyl-;

each R⁵ is independently bromo, chloro, fluoro, methyl, trifluoromethylor vinyl, or

two R⁵ on adjacent carbon atoms together form a —CH═CH—CH═CH— bridge;

each R¹⁰ is independently methyl or hydrogen;

R¹³ is hydrogen or C₁-C₈alkyl.

Yet another group of preferred compounds are those wherein

A¹, A², A³ and A⁴ are independently of each other C—H or C—R⁵,preferably A¹ is C—R⁵, A² is C—H, A³ is C—H and A⁴ is C—H;

G is oxygen;

R¹ is hydrogen;

R² is a group of formula (IIc)

where

m is 0, 1, 2, 3, 4, or 5, and

Y² is S, SO, SO₂, or C═N—OR¹⁰;

R³ is chlorodifluoromethyl or trifluoromethyl;

R⁴ is 3,5-dibromo-phenyl-, 3,5-dichloro-phenyl-,3,5-bis-(trifluoromethyl)-phenyl-, 3,4-dichloro-phenyl-,3,4,5-trichloro-phenyl- or 3-trifluoromethyl-phenyl-;

each R⁵ is independently bromo, chloro, fluoro, methyl, trifluoromethylor vinyl, or two R⁵ on adjacent carbon atoms together form a—CH═CH—CH═CH— bridge;

each R¹⁰ is independently methyl or hydrogen;

R¹³ is methyl.

A further group of preferred compounds are those wherein

A¹ is C—R⁵, A² is C—H, A³ is C—H and A⁴ is C—H;

G is oxygen;

R¹ is hydrogen;

R² is a group of formula (IId)

where

Y² is S, SO, SO₂;

R³ is trifluoromethyl;

R⁴ is 3,5-dichloro-phenyl;

each R⁵ is independently methyl;

R¹³ is hydrogen or methyl.

In one preferred embodiment there is provided a compound of formula (Ia)

where G, R¹, R², R³, R⁴ and R⁵ are as defined for a compound of formula(I); or a salt or N-oxide thereof. The preferred values of G, L, R¹, R²,R³, R⁴, Y¹, Y², Y³, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³ and m are asdefined for a compound of formula (I).

In one preferred embodiment there is provided a compound of formula (Ib)

where G, R¹, R², R³ and R⁴ are as defined for a compound of formula (I);or a salt or N-oxide thereof. The preferred values of G, L, R¹, R², R³,R⁴, Y¹, Y², Y³, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³ and m are as definedfor a compound of formula (I).

In one preferred embodiment there is provided a compound of formula (Ic)

where G, R¹, R², R³, R⁴ and R⁵ are as defined for a compound of formula(I); or a salt or N-oxide thereof. The preferred values of G, L, R¹, R²,R³, R⁴, Y¹, Y², Y³, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³ and m are asdefined for a compound of formula (I).

Certain intermediates are novel and as such form a further aspect of theinvention.

One group of novel intermediates are compounds of formula (IA)

wherein A¹, A², A³, A⁴, R¹, R², R³ and R⁴ are as defined for a compoundof formula (I); G is oxygen and R is C₁-C₆alkoxy. The preferences forA¹, A², A³, A⁴, R¹, R², R³ and R⁴ are the same as the preferences setout for the corresponding substituents of a compound of formula (I).

A further group of novel intermediates are compounds of formula (VA)

wherein A¹, A², A³, A⁴, R³ and R⁴ are as defined for a compound offormula (I); R is C₁-C₆alkoxy; and X^(A) is a leaving group such as ahalogen atom, preferably bromine or chlorine, more preferably bromine.The preferences for A¹, A², A³, A⁴, R³ and R⁴ are the same as thepreferences set out for the corresponding substituents of a compound offormula (I).

A further group of novel intermediates are compounds of formula (XIA)

wherein A¹, A², A³, A⁴, R³ and R⁴ are as defined for a compound offormula (I); each R is independently C₁-C₆alkoxy; G is oxygen and X^(A)is a leaving group such as a halogen atom, preferably bromine orchlorine, more preferably bromine. The preferences for A¹, A², A³, A⁴,R³ and R⁴ are the same as the preferences set out for the correspondingsubstituents of a compound of formula (I).

A further group of novel intermediates are compounds of formula (XVII)

wherein A¹, A², A³, A⁴, R¹ and R² are as defined for a compound offormula (I), R^(1′), R^(2′) and R^(3′) are each independently optionallysubstituted alkyl or optionally substituted phenyl, preferably C₁-C₈alkyl, C₁-C₈ haloalkyl, phenyl or phenyl optionally substituted with oneto five groups independently selected from halogen and C₁-C₈ alkyl,R^(4′) is optionally substituted phenyl, optionally substituted alkyl,preferably C₁-C₈ alkyl or C₁-C₈ haloalkyl. The preferences for A¹, A²,A³, A⁴, R¹ and R² are the same as the preferences set out for thecorresponding substituents of a compound of formula (I).

A further group of novel intermediates are compounds of formula (XX)

wherein A¹, A², A³, A⁴, R¹, R², R³ and R⁴ are as defined for a compoundof formula (I). The preferences for A¹, A², A³, A⁴, R¹, R², R³ and R⁴are the same as the preferences set out for the correspondingsubstituents of a compound of formula (I).

A further group of novel intermediates are compounds of formula (XXIV)

wherein A¹, A², A³, A⁴, R³ and R⁴ are as defined for a compound offormula (I); and X^(A) is a leaving group such as a halogen atom,preferably bromine or chlorine, more preferably bromine. The preferencesfor A¹, A², A³, A⁴, R³ and R⁴ are the same as the preferences set outfor the corresponding substituents of a compound of formula (I).

A further group of novel intermediates are compounds of formula (XXVI)

wherein A¹, A², A³, A⁴, R¹, R², R³ and R⁴ are as defined for a compoundof formula (I); The preferences for A¹, A², A³, A⁴, R¹, R², R³ and R⁴are the same as the preferences set out for the correspondingsubstituents of a compound of formula (I).

A further group of novel intermediates are compounds of formula (XXVII)

wherein A¹, A², A³, A⁴, R³ and R⁴ are as defined for a compound offormula (I); and X^(A) is a leaving group such as a halogen atom,preferably bromine or chlorine, more preferably bromine. The preferencesfor A¹, A², A³, A⁴, R³ and R⁴ are the same as the preferences set outfor the corresponding substituents of a compound of formula (I).

The compounds of the invention may be made by a variety of methods, forexample, as shown in Scheme 1.

1) An amine of formula (IX) where A¹, A², A³ and A⁴ are as defined for acompound of formula (I) and X^(A) is a leaving group, for example ahalogen atom, such as a bromine atom, can be made by reacting abenzonitrile of formula (X) where A¹, A², A³ and A⁴ are as defined for acompound of formula (I) and X^(A) is a leaving group, for example ahalogen atom, such as a bromine atom, with a reducing agent, for examplea metal hydride, such as lithium aluminum hydride, in a solvent, such asan aprotic solvent, such as diethyl ether. The reaction is carried outpreferably under a protective atmosphere, such as an argon atmosphere.The reaction is carried out preferably at a temperature of from −20° C.to +100° C., more preferably from 0° C. to 80° C., in particular at 40°C. Benzonitriles of formula (X) are commercially available or can bemade by methods known to a person skilled in the art. 2) A formamide offormula (VIII) where A¹, A², A³ and A⁴ are as defined for a compound offormula (I) and X^(A) is a leaving group, for example a halogen atom,such as a bromine atom, can be made by reacting an amine of formula (IX)as defined under 1), with a formylating agent, such as ethyl formate, ina solvent, for example an excess of the formylating agent, in thepresence of a base, for example an organic base, such as triethylamine.The reaction is carried out preferably at a temperature of from −20° C.to +100° C., more preferably from 20° C. to 90° C., in particular at thereflux temperature of the solvent.

3) An isocyano compound of formula (VII) where A¹, A², A³ and A⁴ are asdefined for a compound of formula (I) and X^(A) is a leaving group, forexample a halogen atom, such as a bromine atom, can be made by reactinga formamide of formula (VIII) as defined under 2), with a dehydratingagent, for example a chlorinating agent, such as phosphorus oxychloride,in a solvent, for example an aprotic solvent, such as dichloromethane.The reaction is carried out preferably at a temperature of from −20° C.to +50° C., more preferably from 0° C. to 50° C., in particular atambient temperature.

4) A compound of formula (V) where A¹, A², A³, A⁴, R³ and R⁴ are asdefined for a compound of formula (I) and X^(A) is a leaving group, forexample a halogen atom, such as a bromine atom, can be made by reactingan isocyano compound of formula (VII) as defined under 3), with a vinylcompound of formula (VI) where R³ and R⁴ are as defined for a compoundof formula (I), in the presence of a catalyst, such as copper(I) oxide,in a solvent, for example an aromatic solvent, such as toluene. Thereaction is carried out preferably at a temperature of from −20° C. to+200° C., more preferably from 50° C. to 150° C., in particular at 110°C. Vinyl compounds of formula (VI) are known from the literature (forexample, from EP 1,731,512) or can be made by methods known to a personskilled in the art.

5) A carboxylic ester of formula (IV) where A¹, A², A³, A⁴, R³ and R⁴are as defined for a compound of formula (I), G is oxygen and R isC₁-C₈alkoxy, can be made by reacting a compound of formula (V) asdefined under 4), with carbon monoxide and an alcohol of formula R—Hwhere R is C₁-C₈alkoxy, such as ethanol, in the presence of a catalyst,such as bis(triphenylphosphine)palladium(II) dichloride (“Pd(PPh₃)₂Cl₂”)or dichloro 1,1′-bis(diphenylphosphino)ferrocene palladium(II)dichloromethane adduct (“Pd(dppf)Cl₂”), in the presence of a base, suchas pyridine, triethylamine, 4-(dimethylamino)-pyridine (“DMAP”),diisopropylethylamine (Hunig's base) or sodium acetate, and optionallyin the presence of a solvent, for example a polar solvent, such asdimethylformamide. The reaction is carried out preferably at atemperature of from −20° C. to +200° C., more preferably from 50° C. to150° C., in particular at 85° C. The reaction is carried out preferablyat a pressure of from 1 to 200 bar, more preferably from 2 to 10 bar, inparticular at 6 bar.

6) A carboxylic acid of formula (III) where A¹, A², A³, A⁴, R³ and R⁴are as defined for a compound of formula (I), G is oxygen and R is OH,can be made from a carboxylic ester of formula (IV) as defined under 5),under standard conditions, such as treatment with an alkali hydroxide,such as sodium hydroxide or potassium hydroxide, in a solvent, such asethanol or tetrahydrofuran, in the presence of water. Anotheralternative is the treatment of the ester with an acid, such astrifluoroacetic acid, in a solvent, such as dichloromethane, followed byaddition of water. The reaction is carried out preferably at atemperature of from −20° C. to +100° C., more preferably from 20° C. to80° C., in particular at 50° C.

7) An acid halide of formula (III′) where A¹, A², A³, A⁴, R³ and R⁴ areas defined for a compound of formula (I), G is oxygen and R is Br, Cl orF, can be made from a carboxylic acid of formula (III) as defined under5), under standard conditions, such as treatment with thionyl chlorideor oxalyl chloride, in a solvent, such as dichloromethane. The reactionis carried out preferably at a temperature of from −20° C. to +100° C.,more preferably from 0° C. to 50° C., in particular at ambienttemperature.

8) A compound of formula (I) where A¹, A², A³, A⁴, R³ and R⁴ are asdefined for a compound of formula (I) and G is oxygen, can be made byreacting a carboxylic acid of formula (III) or an acid halide of formula(III′) where A¹, A², A³, A⁴, R³ and R⁴ are as defined for a compound offormula (I) and G is oxygen, with an amine of formula HNR¹R² where R¹and R² are as defined for a compound of formula (I). When a carboxylicacid is used, such reactions are usually carried out in the presence ofa coupling reagent, such as N,N′-dicyclohexylcarbodiimide (“DCC”),1-ethyl-3-(3-dimethylamino-propyl)carbodiimide hydrochloride (“EDC”) orbis(2-oxo-3-oxazolidinyl)phosphonic chloride (“BOP-Cl”), in the presenceof a base, and optionally in the presence of a nucleophilic catalyst.Such reactions are carried out preferably at a temperature of from −20°C. to +200° C., more preferably from 50° C. to 150° C., in particular at100° C. When an acid halide is used, such reactions are usually carriedout in the presence of a base, and optionally in the presence of anucleophilic catalyst. Alternatively, when an acid halide is used it ispossible to conduct the reaction in a biphasic system comprising anorganic solvent, preferably ethyl acetate, and an aqueous solvent,preferably a solution of sodium hydrogen carbonate. Such reactions arecarried out preferably at a temperature of from −20° C. to +50° C., morepreferably from 0° C. to 50° C., in particular at ambient temperature.Suitable nucleophilic catalysts include hydroxybenzotriazole (“HOBT”).Suitable solvents include dimethylacetamide, tetrahydrofuran, dioxane,1,2-dimethoxyethane, ethyl acetate and toluene. Amines of formula (II)are known from the literature (for example, from WO 2007/080131) or canbe made by methods known to a person skilled in the art.

9) A compound of formula (I) where A¹, A², A³, A⁴, R¹, R², R³ and R⁴ areas defined for a compound of formula (I) and G is sulfur, can be made byreacting a compound of formula (III) where A¹, A², A³, A⁴, R³ and R⁴ areas defined for a compound of formula (I), G is oxygen, or a compound offormula (III′) wherein R is Br, Cl or F, or a compound of formula (XI)wherein R is C₁-C₈alkoxy (see Scheme 2), with a thio-transfer reagent,such as Lawesson's reagent or phosphorus pentasulfide, prior to reactingwith the amine of formula HNR¹R² as described under 8).

9a) Alternatively a compound of formula (V) where A¹, A², A³, A⁴, R³ andR⁴ are as defined for a compound of formula (I) and X^(A) is a leavinggroup, for example a halogen atom, such as a bromine atom can be made bytreatment of a compound of formula (VA) where A¹, A², A³, A⁴, R³ and R⁴are as defined for a compound of formula (I) and X^(A) is a leavinggroup, for example a halogen atom, such as a bromine atom and R isC₁-C₆alkoxy under hydrolytic conditions followed by decarboxylation ofthe acid intermediate. Such conditions are, for example, treatment withan alkali hydroxide, such as sodium hydroxide or potassium hydroxide, ina solvent, such as ethanol or tetrahydrofuran, in the presence of water.Another alternative is the treatment of the ester with an acid, such astrifluoroacetic acid, in a solvent, such as dichloromethane, followed byaddition of water. The reaction is carried out preferably at atemperature of from −20° C. to +100° C., more preferably from 20° C. to80° C., in particular at 50° C.

9b) A compound of formula (VA) as A¹, A², A³, A⁴, R³ and R⁴ are asdefined for a compound of formula (I) and X^(A) is a leaving group, forexample a halogen atom, such as a bromine atom, can be made by reactingan isocyano compound of formula (VII) as defined under 3), with a vinylcompound of formula (VIA) where R³ and R⁴ are as defined for a compoundof formula (I) and R is C₁-C₆alkoxy, in the presence of a catalyst, suchas copper(I) oxide, in a solvent, for example an aromatic solvent, suchas toluene. The reaction is carried out preferably at a temperature offrom −20° C. to +200° C., more preferably from 50° C. to 150° C., inparticular at 110° C. Vinyl compounds of formula (VIA) are known fromthe literature (for example, from J. Org. Chem. (2003), 68(15),5925-5929) or can be made by methods known to a person skilled in theart.

10) A compound of formula (XIV) where A¹, A², A³, A⁴ are as defined fora compound of formula (I), R is C₁-C₆alkoxy, R^(1′), R^(2′) and R^(3′)represent optionally substituted alkyl or optionally substituted phenyland G is oxygen, can be made by reacting a carboxylic acid of formula(XV) where A¹, A², A³, A⁴ are as defined for a compound of formula (I)and R is C₁-C₆alkoxy, with an amine (XVI) where R^(1′), R^(2′) andR^(3′) represent optionally substituted alkyl or optionally substitutedphenyl. Such reactions are usually carried out in the presence of acoupling reagent, such as N,N′-dicyclohexylcarbodiimide (“DCC”),1-ethyl-3-(3-dimethylamino-propyl)carbodiimide hydrochloride (“EDC”) orbis(2-oxo-3-oxazolidinyl)phosphonic chloride (“BOP-Cl”), in the presenceof a base, and optionally in the presence of a nucleophilic catalyst.Such reactions are carried out preferably at a temperature of from −20°C. to +200° C., more preferably from 50° C. to 150° C., in particular at100° C. Suitable nucleophilic catalysts include hydroxybenzotriazole(“HOBT”). Suitable solvents include dimethylacetamide, tetrahydrofuran,dioxane, 1,2-dimethoxyethane, ethyl acetate and toluene. Amines offormula (XVI) and carboxylic acids of formula (XV) are known from theliterature or can be made by methods known to a person skilled in theart.

11) A compound of formula (XIII) where A¹, A², A³, A⁴ are as defined fora compound of formula (I) R is C₁-C₆alkoxy, R^(1′), R^(2′) and R^(3′)represent optionally substituted alkyl or optionally substituted phenyland G is oxygen can be made by reacting a compound of formula (XIV)where A¹, A², A³, A⁴ are as defined for a compound of formula (I) R isC₁-C₆alkoxy, R^(1′), R^(2′) and R^(3′) represent optionally substitutedalkyl or optionally substituted phenyl and G is oxygen, with athio-transfer reagent, such as Lawesson's reagent or phosphoruspentasulfide in a solvent, for example an aromatic solvent, such astoluene. The reaction is carried out preferably at a temperature of from−20° C. to +200° C., more preferably from 50° C. to 150° C., inparticular at 110° C.

12) A compound of formula (XII) where A¹, A², A³, A⁴ are as defined fora compound of formula (I) R is C₁-C₆alkoxy, R^(1′), R^(2′) and R^(3′)represent optionally substituted alkyl or optionally substituted phenyl,R^(4′) represents optionally substituted alkyl and G is oxygen can bemade by reacting a compound of formula (XIII) where A¹, A², A³, A⁴ areas defined for a compound of formula (I) R is C₁-C₆alkoxy, R^(1′),R^(2′) and R^(3′) represent optionally substituted alkyl or optionallysubstituted phenyl and G is oxygen with an alkylating agent R^(4′)—Xwhere X is a leaving group for example a halogen atom, such as an iodineatom and a base such as sodium carbonate or potassium carbonate in asolvent, such as acetonitrile. The reaction is carried out preferably ata temperature of from −20° C. to +100° C., more preferably from 0° C. to50° C., in particular at ambient temperature.

13) A compound of formula (XI) where A¹, A², A³, A⁴, R¹, R², R³ and R⁴are as defined for a compound of formula (I), G is oxygen and R isC₁-C₆alkoxy can be made by reacting a compound of formula (XII) whereA¹, A², A³, A⁴ are as defined for a compound of formula (I) R isC₁-C₆alkoxy, R^(1′), R^(2′) and R^(3′) represent optionally substitutedalkyl or optionally substituted phenyl, R^(4′) represents optionallysubstituted alkyl and G is oxygen with a vinyl compound of formula (VI)where R³ and R⁴ are as defined for a compound of formula (I), in thepresence of a fluorine reagent such as potassium fluoride ortetrabutylammonium fluoride, in a solvent, for example THF. The reactionis carried out preferably at a temperature of from −20° C. to +500° C.,more preferably from 0° C. to 100° C., in particular at ambienttemperature. Vinyl compounds of formula (VI) are known from theliterature (for example, from EP 1,731,512) or can be made by methodsknown to a person skilled in the art.

14) A compound of formula (I) where A¹, A², A³, A⁴, R¹, R², R³ and R⁴are as defined for a compound of formula (I) and G is oxygen, can bemade by reacting a carboxylic acid of formula (III) or an acid halide offormula (III′) where A¹, A², A³, A⁴, R³ and R⁴ are as defined for acompound of formula (I), G is oxygen and R is Br, Cl or F (which can beobtained from a compound of the formula (XI) where A¹, A², A³, A⁴, R¹,R², R³ and R⁴ are as defined for a compound of formula (I), G is oxygenand R is C₁-C₆alkoxy), with an amine of formula HNR¹R² where R¹ and R²are as defined for a compound of formula (I) under conditions describedunder 8).

14a) Alternatively a compound of formula (III) where A¹, A², A³, A⁴, R³and R⁴ are as defined for a compound of formula (I) and G is Oxygen canbe made by treatment of a compound of formula (XIA) where A¹, A², A³,A⁴, R³ and R⁴ are as defined for a compound of formula (I) and R isC₁-C₆alkoxy under hydrolytic conditions followed by decarboxylation.Such conditions are, for example, treatment with an alkali hydroxide,such as sodium hydroxide or potassium hydroxide, in a solvent, such asethanol or tetrahydrofuran, in the presence of water. Anotheralternative is the treatment of the ester with an acid, such astrifluoroacetic acid, in a solvent, such as dichloromethane, followed byaddition of water. The reaction is carried out preferably at atemperature of from −20° C. to +100° C., more preferably from 20° C. to80° C., in particular at 50° C.

14b) A compound of formula (XIA) where A¹, A², A³, A⁴, R³ and R⁴ are asdefined for a compound of formula (I) and R is C₁-C₆alkoxy, can be madereacting a compound of formula (XII) where A¹, A², A³, A⁴ are as definedfor a compound of formula (I) R is C₁-C₆alkoxy, R^(1′), R^(2′) andR^(3′) represent optionally substituted alkyl or optionally substitutedphenyl, R^(4′) represents optionally substituted alkyl and G is oxygenwith a vinyl compound of formula (VIA) where R³ and R⁴ are as definedfor a compound of formula (I) and R is C₁-C₆alkoxy, in the presence of afluorine reagent such as potassium fluoride or tetrabutylammoniumfluoride, in a solvent, for example THF. The reaction is carried outpreferably at a temperature of from −20° C. to +500° C., more preferablyfrom 0° C. to 100° C., in particular at ambient temperature. Vinylcompounds of formula (VIA) are known from the literature (for example,from J. Org. Chem. (2003), 68(15), 5925-5929) or can be made by methodsknown to a person skilled in the art.

15) Carboxylic acids of formula (XVIII) where A¹, A², A³, A⁴ are asdefined for a compound of formula (I), R^(1′), R^(2′) and R^(3′)represent optionally substituted alkyl or optionally substituted phenyl,R^(4′) represents optionally substituted alkyl and G is oxygen may beformed from esters of formula (XII), wherein R is C₁-C₆alkoxy. It isknown to a person skilled in the art that there are many methods for thehydrolysis of such esters depending on the nature of the alkoxy group.One widely used method to achieve such a transformation is the treatmentof the ester with an alkali hydroxide, such as sodium hydroxide orlithium hydroxide, in a solvent, such as ethanol or tetrahydrofuran, inthe presence of water. Another is the treatment of the ester with anacid, such as trifluoroacetic acid, in a solvent, such asdichloromethane, followed by addition of water. The reaction is carriedout at temperatures of from 0° C. to 150° C., preferably from 15° C. to100° C., in particular at 50° C.

16) A compound of formula (XVII) where A¹, A², A³, A⁴ are as defined fora compound of formula (I), R^(1′), R^(2′) and R^(3′) representoptionally substituted alkyl or optionally substituted phenyl, R^(4′)represents optionally substituted alkyl and G is oxygen may be formed byreaction of acids of formula (XVIII) where A¹, A², A³, A⁴ are as definedfor a compound of formula (I), R^(1′), R^(2′) and R^(3′) representoptionally substituted alkyl or optionally substituted phenyl, R^(4′)represents optionally substituted alkyl and G is oxygen with an amine offormula HNR¹R² where R¹ and R² are as defined for a compound of formula(I) under conditions described under 8).

17) A compound of formula (I) where A¹, A², A³, A⁴, R¹, R², R³ and R⁴are as defined for a compound of formula (I) and G is oxygen, can bemade by reacting a compound of the formula (XVII) where A¹, A², A³, A⁴,R¹, R², R³ and R⁴ are as defined for a compound of formula (I), G isoxygen, R^(1′), R^(2′) and R^(3′) represent optionally substituted alkylor optionally substituted phenyl and R^(4′) represents optionallysubstituted alkyl with a vinyl compound of formula (VI) where R³ and R⁴are as defined for a compound of formula (I), in the presence of afluorine reagent such as potassium fluoride or tetrabutylammoniumfluoride, in a solvent, for example THF under conditions described under13).

17a) Alternatively a compound of formula (I) where A¹, A², A³, A⁴, R³and R⁴ are as defined herein and G is oxygen can be made by treatment ofa compound of formula (IA) where A¹, A², A³, A⁴, R³ and R⁴ are asdefined for a compound of formula (I), G is oxygen, and R isC₁-C₆alkoxy, under hydrolytic conditions followed by decarboxylation.Such conditions are, for example, treatment with an alkali hydroxide,such as sodium hydroxide or potassium hydroxide, in a solvent, such asethanol or tetrahydrofuran, in the presence of water. Anotheralternative is the treatment of the ester with an acid, such astrifluoroacetic acid, in a solvent, such as dichloromethane, followed byaddition of water. The reaction is carried out preferably at atemperature of from −20° C. to +100° C., more preferably from 20° C. to80° C., in particular at 50° C.

17b) A compound of formula (IA) where A¹, A², A³, A⁴, R³ and R⁴ are asdefined for a compound of formula (I), G is oxygen, and R isC₁-C₆alkoxy, can be made reacting a compound of formula (XVII) where A¹,A², A³, A⁴ are as defined for a compound of formula (I), R^(1′), R^(2′)and R^(3′) represent optionally substituted alkyl or optionallysubstituted phenyl, R^(4′) represents optionally substituted alkyl and Gis oxygen with a vinyl compound of formula (VIA) where R³ and R⁴ are asdefined for a compound of formula (I) and R is C₁-C₆alkoxy, in thepresence of a fluorine reagent such as potassium fluoride ortetrabutylammonium fluoride, in a solvent, for example THF. The reactionis carried out preferably at a temperature of from −20° C. to +500° C.,more preferably from 0° C. to 100° C., in particular at ambienttemperature. Vinyl compounds of formula (VIA) are known from theliterature (for example, from J. Org. Chem. (2003), 68(15), 5925-5929)or can be made by methods known to a person skilled in the art.

18) A compound of formula (I) where A¹, A², A³, A⁴, R¹, R², R³ and R⁴are as defined herein and G is oxygen, can be made by reacting acompound of the formula (XX) where A¹, A², A³, A⁴, R¹, R², R³ and R⁴ areas defined for a compound of formula (I) and G is oxygen, with areducing agent such as Zn/HCl, in a solvent, for example water or DMF ormixtures thereof. The reaction is carried out preferably at atemperature of from −20° C. to +500° C., more preferably from 0° C. to100° C., in particular at 80° C.

19) A compound of formula (XX) where A¹, A², A³, A⁴, R¹, R², R³ and R⁴are as defined for a compound of formula (I) and G is oxygen, can bemade by reacting a compound of the formula (XXI) where A¹, A², A³, A⁴,R¹, R², R³ and R⁴ are as defined for a compound of formula (I) and G isoxygen (which may be prepared according to the methods described in WO2009/080250) with nitromethane in the presence of a base such as NaOH,in a solvent, for example water or DMF or mixtures thereof. The reactionis carried out preferably at a temperature of from −20° C. to +500° C.,more preferably from 0° C. to 100° C., in particular at ambienttemperature.

20) Alternatively, a compound of formula (I) where A¹, A², A³, A⁴, R¹,R², R³ and R⁴ are as defined herein and G is oxygen, as shown in Scheme4 can be prepared from a compound of the formula (XX) where A¹, A², A³,A⁴, R¹, R², R³ and R⁴ are as defined for a compound of formula (I) and Gis oxygen via an intermediate (XIX) where A¹, A², A³, A⁴, R¹, R², R³ andR⁴ are as defined for a compound of formula (I) and G is oxygen, forexample under reaction conditions described under 18).

Representative experimental conditions for this transformation are alsodescribed in Tetrahedron Letters 2003, 44, 3701-3703.

21) A compound of formula (III) where A¹, A², A³, A⁴, R³ and R⁴ are asdefined for a compound of formula (I), G is oxygen can be made from ancompound of the formula (XI) where A¹, A², A³, A⁴, R³ and R⁴ are asdefined for a compound of formula (I), G is oxygen and R is C₁-C₆alkoxyunder conditions described under 6) 22) A compound of formula (XI) whereA¹, A², A³, A⁴, R³ and R⁴ are as defined for a compound of formula (I),G is oxygen and R is C₁-C₆alkoxy can be made by reacting a compound offormula (XXII) where A¹, A², A³, A⁴, R¹, R², R³ and R⁴ are as definedfor a compound of formula (I) and X^(A) is a leaving group, for examplea halogen atom, such as a bromine atom and G is oxygen as describedunder 5).

23) A compound of formula (XXII) where A¹, A², A³, A⁴, R³ and R⁴ are asdefined for a compound of formula (I) and X^(A) is a leaving group, forexample a halogen atom, such as a bromine atom and G is oxygen, can bemade by reacting a compound of the formula (XXIV) where A¹, A², A³, A⁴,R³ and R⁴ are as defined for a compound of formula (I) and X^(A) is aleaving group, for example a halogen atom, such as a bromine atom and Gis oxygen under conditions as described under 18).

24) Alternatively, compounds of formula (XXII) where A¹, A², A³, A⁴, R³and R⁴ are as defined for a compound of formula (I) and X^(A) is aleaving group, for example a halogen atom, such as a bromine atom and Gis oxygen, as shown in Scheme 5 can be prepared from a compound of theformula (XXIV) where A¹, A², A³, A⁴, R³ and R⁴ are as defined for acompound of formula (I) and X^(A) is a leaving group, for example ahalogen atom, such as a bromine atom and G is oxygen via an intermediate(XIII) where A¹, A², A³, A⁴, R³ and R⁴ are as defined for a compound offormula (I) and X^(A) is a leaving group, for example a halogen atom,such as a bromine atom and G is oxygen for example under reactionconditions described under 18).

25) A compound of formula (XXIV) where A¹, A², A³, A⁴, R³ and R⁴ are asdefined for a compound of formula (I) and X^(A) is a leaving group, forexample a halogen atom, such as a bromine atom and G is oxygen, can bemade by reacting a compound of the formula (XXV) where A¹, A², A³, A⁴,R³ and R⁴ are as defined for a compound of formula (I) and X^(A) is aleaving group, for example a halogen atom, such as a bromine atom and Gis oxygen (which may be prepared according to the methods described inWO 2009/080250) under conditions as described under 19).

26) Alternatively, a compound of formula (I) where A¹, A², A³, A⁴, R¹,R², R³ and R⁴ are as defined for a compound of formula (I) and G isoxygen, can be made by reacting a compound of the formula (XXVI) whereA¹, A², A³, A⁴, R¹, R², R³ and R⁴ are as defined for a compound offormula (I) and G is oxygen, with a reducing agent such as Raney Ni/H₂,in a solvent, for example methanol or ethanol. The reaction is carriedout preferably at a temperature of from −20° C. to +500° C., morepreferably from 0° C. to 100° C. Representative experimental conditionsfor this transformation are described by Allen, C. F. H. and Wilson, C.V. in Org Synth. (1947), 27.

27) A compound of formula (XXVI) where A¹, A², A³, A⁴, R¹, R², R³ and R⁴are as defined for a compound of formula (I) and G is oxygen, can bemade by reacting a compound of the formula (XXI) where A¹, A², A³, A⁴,R¹, R², R³ and R⁴ are as defined for a compound of formula (I) and G isoxygen (which may be prepared according to the methods described in WO2009/080250) with a cyanide source such as sodium cyanide, potassiumcyanide, trimethylsilyl cyanide, acetone cyanohydrin, ordiethylaluminium cyanide, in a solvent, for example toluene,tetrahydrofuran, acetone, acetic acid, ethanol, or water or mixturesthereof. The reaction is carried out preferably at a temperature of from−20° C. to +500° C., more preferably from 0° C. to 100° C., inparticular at ambient temperature. Representative experimentalconditions for this transformation are described in Tetrahedron, 64(17),3642-3654; 2008.

28) A compound of formula (XXII) where A¹, A², A³, A⁴, R³ and R⁴ are asdefined for a compound of formula (I) and X^(A) is a leaving group, forexample a halogen atom, such as a bromine atom and G is oxygen, can bemade by reacting a compound of the formula (XXVII) where A¹, A², A³, A⁴,R³ and R⁴ are as defined for a compound of formula (I) and X^(A) is aleaving group, for example a halogen atom, such as a bromine atom and Gis oxygen (which may be prepared according to the methods described inWO 2009/080250) under conditions as described under 26).

29) A compound of formula (XXVII) where A¹, A², A³, A⁴, R³ and R⁴ are asdefined for a compound of formula (I) and X^(A) is a leaving group, forexample a halogen atom, such as a bromine atom and G is oxygen, can bemade by reacting a compound of the formula (XXV) where A¹, A², A³, A⁴,R³ and R⁴ are as defined for a compound of formula (I) and X^(A) is aleaving group, for example a halogen atom, such as a bromine atom and Gis oxygen under conditions as described under 27).

Compounds of formula (I) contain a chiral centre giving rise toenantiomers of the formula (I*) and (I**).

Enantiomerically enriched mixtures of compounds of formula (I*) or (I**)may be prepared, for example, according to schemes 4 or 5 by formationof intermediate XX or XXIV via an asymmetric Michael addition, see forexample J. Org. Chem. 2008, 73, 3475-3480 and references cited therein”.Alternatively, such enantiomerically enriched mixtures may be preparedaccording to schemes 6 or 7 by stereoselective addition of cyanide, seefor example J. Am. Chem. Soc. 2008, 130, 6072-6073.

A compound of formula (I) may be a mixture of compounds I* and I** inany ratio e.g. in a molar ratio of 1:99 to 99:1, e.g. 10:1 to 1:10, e.g.a substantially 50:50 molar ratio. For example, in an enantiomericallyenriched mixture of formula I**, the molar proportion of compound I**compared to the total amount of both enantiomers is for example greaterthan 50%, e.g. at least 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98,or at least 99%. Likewise, in an enantiomerically enriched mixture offormula I*, the molar proportion of the compound of formula I* comparedto the total amount of both enantiomers is for example greater than 50%,e.g. at least 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or atleast 99%.

The compounds of formula (I) can be used to control infestations ofinsect pests such as Lepidoptera, Diptera, Hemiptera, Thysanoptera,Orthoptera, Dictyoptera, Coleoptera, Siphonaptera, Hymenoptera andIsoptera and also other invertebrate pests, for example, acarine,nematode and mollusc pests. Insects, acarines, nematodes and molluscsare hereinafter collectively referred to as pests. The pests which maybe controlled by the use of the invention compounds include those pestsassociated with agriculture (which term includes the growing of cropsfor food and fiber products), horticulture and animal husbandry,companion animals, forestry and the storage of products of vegetableorigin (such as fruit, grain and timber); those pests associated withthe damage of man-made structures and the transmission of diseases ofman and animals; and also nuisance pests (such as flies).

The compounds of the invention may be used for example on turf,ornamentals, such as flowers, shrubs, broad-leaved trees or evergreens,for example conifers, as well as for tree injection, pest management andthe like.

Examples of pest species which may be controlled by the compounds offormula (I) include: Myzus persicae (aphid), Aphis gossypii (aphid),Aphis fabae (aphid), Lygus spp. (capsids), Dysdercus spp. (capsids),Nilaparvata lugens (planthopper), Nephotettixc incticeps (leafhopper),Nezara spp. (stinkbugs), Euschistus spp. (stinkbugs), Leptocorisa spp.(stinkbugs), Frankliniella occidentalis (thrip), Thrips spp. (thrips),Leptinotarsa decemlineata (Colorado potato beetle), Anthonomus grandis(boll weevil), Aonidiella spp. (scale insects), Trialeurodes spp. (whiteflies), Bemisia tabaci (white fly), Ostrinia nubilalis (European cornborer), Spodoptera littoralis (cotton leafworm), Heliothis virescens(tobacco budworm), Helicoverpa armigera (cotton bollworm), Helicoverpazea (cotton bollworm), Sylepta derogata (cotton leaf roller), Pierisbrassicae (white butterfly), Plutella xylostella (diamond back moth),Agrotis spp. (cutworms), Chilo suppressalis (rice stem borer), Locustamigratoria (locust), Chortiocetes terminifera (locust), Diabrotica spp.(rootworms), Panonychus ulmi (European red mite), Panonychus citri(citrus red mite), Tetranychus urticae (two-spotted spider mite),Tetranychus cinnabarinus (carmine spider mite), Phyllocoptruta oleivora(citrus rust mite), Polyphagotarsonemus latus (broad mite), Brevipalpusspp. (flat mites), Boophilus microplus (cattle tick), Dermacentorvariabilis (American dog tick), Ctenocephalides felis (cat flea),Liriomyza spp. (leafminer), Musca domestica (housefly), Aedes aegypti(mosquito), Anopheles spp. (mosquitoes), Culex spp. (mosquitoes),Lucillia spp. (blowflies), Blattella germanica (cockroach), Periplanetaamericana (cockroach), Blatta orientalis (cockroach), termites of theMastotermitidae (for example Mastotermes spp.), the Kalotermitidae (forexample Neotermes spp.), the Rhinotermitidae (for example Coptotermesformosanus, Reticulitermes flavipes, R. speratu, R. virginicus, R.hesperus, and R. santonensis) and the Termitidae (for exampleGlobitermes sulfureus), Solenopsis geminata (fire ant), Monomoriumpharaonis (pharaoh's ant), Damalinia spp. and Linognathus spp. (bitingand sucking lice), Meloidogyne spp. (root knot nematodes), Globoderaspp. and Heterodera spp. (cyst nematodes), Pratylenchus spp. (lesionnematodes), Rhodopholus spp. (banana burrowing nematodes), Tylenchulusspp. (citrus nematodes), Haemonchus contortus (barber pole worm),Caenorhabditis elegans (vinegar eelworm), Trichostrongylus spp. (gastrointestinal nematodes) and Deroceras reticulatum (slug).

The invention therefore provides a method of controlling insects,acarines, nematodes or molluscs which comprises applying aninsecticidally, acaricidally, nematicidally or molluscicidally effectiveamount of a compound of formula (I), or a composition containing acompound of formula (I), to a pest, a locus of pest, preferably a plant,or to a plant susceptible to attack by a pest. The compounds of formula(I) are preferably used against insects or acarines. The compounds ofthe invention may also be used for controlling insects that areresistant to known insecticides.

The term “plant” as used herein includes seedlings, bushes and trees.

Crops are to be understood as also including those crops which have beenrendered tolerant to herbicides or classes of herbicides (e.g. ALS-,GS-, EPSPS-, PPO- and HPPD-inhibitors) by conventional methods ofbreeding or by genetic engineering. An example of a crop that has beenrendered tolerant to imidazolinones, e.g. imazamox, by conventionalmethods of breeding is Clearfield® summer rape (canola). Examples ofcrops that have been rendered tolerant to herbicides by geneticengineering methods include e.g. glyphosate- and glufosinate-resistantmaize varieties commercially available under the trade names

RoundupReady® and LibertyLink®.

Crops are also to be understood as being those which have been renderedresistant to harmful insects by genetic engineering methods, for exampleBt maize (resistant to European corn borer), Bt cotton (resistant tocotton boll weevil) and also Bt potatoes (resistant to Colorado beetle).Examples of Bt maize are the Bt 176 maize hybrids of NK® (SyngentaSeeds). Examples of transgenic plants comprising one or more genes thatcode for an insecticidal resistance and express one or more toxins areKnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard®(cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®.

Plant crops or seed material thereof can be both resistant to herbicidesand, at the same time, resistant to insect feeding (“stacked” transgenicevents). For example, seed can have the ability to express aninsecticidal Cry3 protein while at the same time being tolerant toglyphosate.

Crops are also to be understood as being those which are obtained byconventional methods of breeding or genetic engineering and containso-called output traits (e.g. improved storage stability, highernutritional value and improved flavor).

In order to apply a compound of formula (I) as an insecticide,acaricide, nematicide or molluscicide to a pest, a locus of pest, or toa plant susceptible to attack by a pest, a compound of formula (I) isusually formulated into a composition which includes, in addition to thecompound of formula (I), a suitable inert diluent or carrier and,optionally, a surface active agent (SFA). SFAs are chemicals which areable to modify the properties of an interface (for example,liquid/solid, liquid/air or liquid/liquid interfaces) by lowering theinterfacial tension and thereby leading to changes in other properties(for example dispersion, emulsification and wetting). It is preferredthat all compositions (both solid and liquid formulations) comprise, byweight, 0.0001 to 95%, more preferably 1 to 85%, for example 5 to 60%,of a compound of formula (I). The composition is generally used for thecontrol of pests such that a compound of formula (I) is applied at arate of from 0.1 g to 10 kg per hectare, preferably from 1 g to 6 kg perhectare, more preferably from 1 g to 1 kg per hectare.

When used in a seed dressing, a compound of formula (I) is used at arate of 0.0001 g to 10 g (for example 0.001 g or 0.05 g), preferably0.005 g to 10 g, more preferably 0.005 g to 4 g, per kilogram of seed.

In another aspect the present invention provides an insecticidal,acaricidal, nematicidal or molluscicidal composition comprising aninsecticidally, acaricidally, nematicidally or molluscicidally effectiveamount of a compound of formula (I) and for example a suitable carrieror diluent therefor. The composition is preferably an insecticidal oracaricidal composition.

The compositions can be chosen from a number of formulation types,including dustable powders (DP), soluble powders (SP), water solublegranules (SG), water dispersible granules (WG), wettable powders (WP),granules (GR) (slow or fast release), soluble concentrates (SL), oilmiscible liquids (OL), ultra low volume liquids (UL), emulsifiableconcentrates (EC), dispersible concentrates (DC), emulsions (both oil inwater (EW) and water in oil (EO)), micro-emulsions (ME), suspensionconcentrates (SC), aerosols, fogging/smoke formulations, capsulesuspensions (CS) and seed treatment formulations. The formulation typechosen in any instance will depend upon the particular purpose envisagedand the physical, chemical and biological properties of the compound offormula (I).

Dustable powders (DP) may be prepared by mixing a compound of formula(I) with one or more solid diluents (for example natural clays, kaolin,pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk,diatomaceous earths, calcium phosphates, calcium and magnesiumcarbonates, sulfur, lime, flours, talc and other organic and inorganicsolid carriers) and mechanically grinding the mixture to a fine powder.

Soluble powders (SP) may be prepared by mixing a compound of formula (I)with one or more water-soluble inorganic salts (such as sodiumbicarbonate, sodium carbonate or magnesium sulfate) or one or morewater-soluble organic solids (such as a polysaccharide) and, optionally,one or more wetting agents, one or more dispersing agents or a mixtureof said agents to improve water dispersibility/solubility. The mixtureis then ground to a fine powder. Similar compositions may also begranulated to form water soluble granules (SG).

Wettable powders (WP) may be prepared by mixing a compound of formula(I) with one or more solid diluents or carriers, one or more wettingagents and, preferably, one or more dispersing agents and, optionally,one or more suspending agents to facilitate the dispersion in liquids.The mixture is then ground to a fine powder. Similar compositions mayalso be granulated to form water dispersible granules (WG).

Granules (GR) may be formed either by granulating a mixture of acompound of formula (I) and one or more powdered solid diluents orcarriers, or from pre-formed blank granules by absorbing a compound offormula (I) (or a solution thereof, in a suitable agent) in a porousgranular material (such as pumice, attapulgite clays, fuller's earth,kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing acompound of formula (I) (or a solution thereof, in a suitable agent) onto a hard core material (such as sands, silicates, mineral carbonates,sulfates or phosphates) and drying if necessary. Agents which arecommonly used to aid absorption or adsorption include solvents (such asaliphatic and aromatic petroleum solvents, alcohols, ethers, ketones andesters) and sticking agents (such as polyvinyl acetates, polyvinylalcohols, dextrins, sugars and vegetable oils). One or more otheradditives may also be included in granules (for example an emulsifyingagent, wetting agent or dispersing agent).

Dispersible Concentrates (DC) may be prepared by dissolving a compoundof formula (I) in water or an organic solvent, such as a ketone, alcoholor glycol ether. These solutions may contain a surface active agent (forexample to improve water dilution or prevent crystallization in a spraytank).

Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may beprepared by dissolving a compound of formula (I) in an organic solvent(optionally containing one or more wetting agents, one or moreemulsifying agents or a mixture of said agents). Suitable organicsolvents for use in ECs include aromatic hydrocarbons (such asalkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100,SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark),ketones (such as cyclohexanone or methylcyclohexanone) and alcohols(such as benzyl alcohol, furfuryl alcohol or butanol),N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone),dimethyl amides of fatty acids (such as C₈-C₁₀ fatty acid dimethylamide)and chlorinated hydrocarbons. An EC product may spontaneously emulsifyon addition to water, to produce an emulsion with sufficient stabilityto allow spray application through appropriate equipment. Preparation ofan EW involves obtaining a compound of formula (I) either as a liquid(if it is not a liquid at room temperature, it may be melted at areasonable temperature, typically below 70° C.) or in solution (bydissolving it in an appropriate solvent) and then emulsifiying theresultant liquid or solution into water containing one or more SFAs,under high shear, to produce an emulsion. Suitable solvents for use inEWs include vegetable oils, chlorinated hydrocarbons (such aschlorobenzenes), aromatic solvents (such as alkylbenzenes oralkylnaphthalenes) and other appropriate organic solvents which have alow solubility in water.

Microemulsions (ME) may be prepared by mixing water with a blend of oneor more solvents with one or more SFAs, to produce spontaneously athermodynamically stable isotropic liquid formulation. A compound offormula (I) is present initially in either the water or the solvent/SFAblend. Suitable solvents for use in MEs include those hereinbeforedescribed for use in ECs or in EWs. An ME may be either an oil-in-wateror a water-in-oil system (which system is present may be determined byconductivity measurements) and may be suitable for mixing water-solubleand oil-soluble pesticides in the same formulation. An ME is suitablefor dilution into water, either remaining as a microemulsion or forminga conventional oil-in-water emulsion.

Suspension concentrates (SC) may comprise aqueous or non-aqueoussuspensions of finely divided insoluble solid particles of a compound offormula (I). SCs may be prepared by ball or bead milling the solidcompound of formula (I) in a suitable medium, optionally with one ormore dispersing agents, to produce a fine particle suspension of thecompound. One or more wetting agents may be included in the compositionand a suspending agent may be included to reduce the rate at which theparticles settle. Alternatively, a compound of formula (I) may be drymilled and added to water, containing agents hereinbefore described, toproduce the desired end product.

Aerosol formulations comprise a compound of formula (I) and a suitablepropellant (for example n-butane). A compound of formula (I) may also bedissolved or dispersed in a suitable medium (for example water or awater miscible liquid, such as n-propanol) to provide compositions foruse in non-pressurized, hand-actuated spray pumps.

A compound of formula (I) may be mixed in the dry state with apyrotechnic mixture to form a composition suitable for generating, in anenclosed space, a smoke containing the compound.

Capsule suspensions (CS) may be prepared in a manner similar to thepreparation of EW formulations but with an additional polymerizationstage such that an aqueous dispersion of oil droplets is obtained, inwhich each oil droplet is encapsulated by a polymeric shell and containsa compound of formula (I) and, optionally, a carrier or diluenttherefor. The polymeric shell may be produced by either an interfacialpolycondensation reaction or by a coacervation procedure. Thecompositions may provide for controlled release of the compound offormula (I) and they may be used for seed treatment. A compound offormula (I) may also be formulated in a biodegradable polymeric matrixto provide a slow, controlled release of the compound.

A composition may include one or more additives to improve thebiological performance of the composition (for example by improvingwetting, retention or distribution on surfaces; resistance to rain ontreated surfaces; or uptake or mobility of a compound of formula (I)).Such additives include surface active agents, spray additives based onoils, for example certain mineral oils or natural plant oils (such assoy bean and rape seed oil), and blends of these with otherbio-enhancing adjuvants (ingredients which may aid or modify the actionof a compound of formula (I)).

A compound of formula (I) may also be formulated for use as a seedtreatment, for example as a powder composition, including a powder fordry seed treatment (DS), a water soluble powder (SS) or a waterdispersible powder for slurry treatment (WS), or as a liquidcomposition, including a flowable concentrate (FS), a solution (LS) or acapsule suspension (CS). The preparations of DS, SS, WS, FS and LScompositions are very similar to those of, respectively, DP, SP, WP, SCand DC compositions described above. Compositions for treating seed mayinclude an agent for assisting the adhesion of the composition to theseed (for example a mineral oil or a film-forming barrier).

Wetting agents, dispersing agents and emulsifying agents may be surfaceSFAs of the cationic, anionic, amphoteric or non-ionic type.

Suitable SFAs of the cationic type include quaternary ammonium compounds(for example cetyltrimethyl ammonium bromide), imidazolines and aminesalts.

Suitable anionic SFAs include alkali metals salts of fatty acids, saltsof aliphatic monoesters of sulfuric acid (for example sodium laurylsulfate), salts of sulfonated aromatic compounds (for example sodiumdodecylbenzenesulfonate, calcium dodecylbenzenesulfonate,butylnaphthalene sulfonate and mixtures of sodium di-isopropyl- andtri-isopropyl-naphthalene sulfonates), ether sulfates, alcohol ethersulfates (for example sodium laureth-3-sulfate), ether carboxylates (forexample sodium laureth-3-carboxylate), phosphate esters (products fromthe reaction between one or more fatty alcohols and phosphoric acid(predominately mono-esters) or phosphorus pentoxide (predominatelydi-esters), for example the reaction between lauryl alcohol andtetraphosphoric acid; additionally these products may be ethoxylated),sulfosuccinamates, paraffin or olefine sulfonates, taurates andlignosulfonates.

Suitable SFAs of the amphoteric type include betaines, propionates andglycinates.

Suitable SFAs of the non-ionic type include condensation products ofalkylene oxides, such as ethylene oxide, propylene oxide, butylene oxideor mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetylalcohol) or with alkylphenols (such as octylphenol, nonylphenol oroctylcresol); partial esters derived from long chain fatty acids orhexitol anhydrides; condensation products of said partial esters withethylene oxide; block polymers (comprising ethylene oxide and propyleneoxide); alkanolamides; simple esters (for example fatty acidpolyethylene glycol esters); amine oxides (for example lauryl dimethylamine oxide); and lecithins.

Suitable suspending agents include hydrophilic colloids (such aspolysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose)and swelling clays (such as bentonite or attapulgite).

A compound of formula (I) may be applied by any of the known means ofapplying pesticidal compounds. For example, it may be applied,formulated or unformulated, to the pests or to a locus of the pests(such as a habitat of the pests, or a growing plant liable toinfestation by the pests) or to any part of the plant, including thefoliage, stems, branches or roots, to the seed before it is planted orto other media in which plants are growing or are to be planted (such assoil surrounding the roots, the soil generally, paddy water orhydroponic culture systems), directly or it may be sprayed on, dustedon, applied by dipping, applied as a cream or paste formulation, appliedas a vapor or applied through distribution or incorporation of acomposition (such as a granular composition or a composition packed in awater-soluble bag) in soil or an aqueous environment.

A compound of formula (I) may also be injected into plants or sprayedonto vegetation using electrodynamic spraying techniques or other lowvolume methods, or applied by land or aerial irrigation systems.

Compositions for use as aqueous preparations (aqueous solutions ordispersions) are generally supplied in the form of a concentratecontaining a high proportion of the active ingredient, the concentratebeing added to water before use. These concentrates, which may includeDCs, SCs, ECs, EWs, MEs, SGs, SPs, WPs, WGs and CSs, are often requiredto withstand storage for prolonged periods and, after such storage, tobe capable of addition to water to form aqueous preparations whichremain homogeneous for a sufficient time to enable them to be applied byconventional spray equipment. Such aqueous preparations may containvarying amounts of a compound of formula (I) (for example 0.0001 to 10%,by weight) depending upon the purpose for which they are to be used.

A compound of formula (I) may be used in mixtures with fertilizers (forexample nitrogen-, potassium- or phosphorus-containing fertilizers).Suitable formulation types include granules of fertilizer. The mixturespreferably contain up to 25% by weight of the compound of formula (I).

The invention therefore also provides a fertilizer compositioncomprising a fertilizer and a compound of formula (I).

The compositions of this invention may contain other compounds havingbiological activity, for example micronutrients or compounds havingfungicidal activity or which possess plant growth regulating,herbicidal, insecticidal, nematicidal or acaricidal activity.

The compound of formula (I) may be the sole active ingredient of thecomposition or it may be admixed with one or more additional activeingredients such as a pesticide, fungicide, synergist, herbicide orplant growth regulator where appropriate. An additional activeingredient may: provide a composition having a broader spectrum ofactivity or increased persistence at a locus; synergize the activity orcomplement the activity (for example by increasing the speed of effector overcoming repellency) of the compound of formula (I); or help toovercome or prevent the development of resistance to individualcomponents. The particular additional active ingredient will depend uponthe intended utility of the composition. Examples of suitable pesticidesinclude the following:

a) Pyrethroids, such as permethrin, cypermethrin, fenvalerate,esfenvalerate, deltamethrin, cyhalothrin (in particularlambda-cyhalothrin, gamma-cyhalothrin), bifenthrin, fenpropathrin,cyfluthrin, tefluthrin, fish safe pyrethroids (for example ethofenprox),natural pyrethrin, tetramethrin, S-bioallethrin, fenfluthrin,prallethrin or5-benzyl-3-furylmethyl-(E)-(1R,3S)-2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate;b) Organophosphates, such as profenofos, sulprofos, acephate, methylparathion, azinphos-methyl, demeton-s-methyl, heptenophos, thiometon,fenamiphos, monocrotophos, profenofos, triazophos, methamidophos,dimethoate, phosphamidon, malathion, chlorpyrifos, phosalone, terbufos,fensulfothion, fonofos, phorate, phoxim, pirimiphos-methyl,pirimiphos-ethyl, fenitrothion, fosthiazate or diazinon;c) Carbamates (including aryl carbamates), such as pirimicarb,triazamate, cloethocarb, carbofuran, furathiocarb, ethiofencarb,aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur,methomyl or oxamyl;d) Benzoyl ureas, such as diflubenzuron, triflumuron, hexaflumuron,flufenoxuron or chlorfluazuron;e) Organic tin compounds, such as cyhexatin, fenbutatin oxide orazocyclotin;f) Pyrazoles, such as tebufenpyrad and fenpyroximate;g) Macrolides, such as avermectins or milbemycins, for exampleabamectin, emamectin benzoate, ivermectin, milbemycin, spinosad,azadirachtin or spinetoram;h) Hormones or pheromones;i) Organochlorine compounds, such as endosulfan (in particularalpha-endosulfan), benzene hexachloride, DDT, chlordane or dieldrin;j) Amidines, such as chlordimeform or amitraz;k) Fumigant agents, such as chloropicrin, dichloropropane, methylbromide or metam;l) Neonicotinoid compounds, such as imidacloprid, thiacloprid,acetamiprid, nitenpyram, dinotefuran, thiamethoxam, clothianidin,nithiazine or flonicamid;m) Diacylhydrazines, such as tebufenozide, chromafenozide ormethoxyfenozide;n) Diphenyl ethers, such as diofenolan or pyriproxifen;

o) Indoxacarb; p) Chlorfenapyr; q) Pymetrozine;

r) Spirotetramat, spirodiclofen or spiromesifen;s) Diamides, such as flubendiamide, chlorantraniliprole orcyantraniliprole;

t) Sulfoxaflor; u) Metaflumizone; v) Fipronil and Ethiprole; or w)Pyrifluqinazon.

In addition to the major chemical classes of pesticide listed above,other pesticides having particular targets may be employed in thecomposition, if appropriate for the intended utility of the composition.For instance, selective insecticides for particular crops, for examplestemborer specific insecticides (such as cartap) or hopper specificinsecticides (such as buprofezin) for use in rice may be employed.Alternatively insecticides or acaricides specific for particular insectspecies/stages may also be included in the compositions (for exampleacaricidal ovo-larvicides, such as clofentezine, flubenzimine,hexythiazox or tetradifon; acaricidal motilicides, such as dicofol orpropargite; acaricides, such as bromopropylate or chlorobenzilate; orgrowth regulators, such as hydramethylnon, cyromazine, methoprene,chlorfluazuron or diflubenzuron).

Examples of fungicidal compounds which may be included in thecomposition of the invention are(E)-N-methyl-2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxy-iminoacetamide(SSF-129),4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethyl-benzimidazole-1-sulfonamide,α-[N-(3-chloro-2,6-xylyl)-2-methoxyacetamido]-γ-butyrolactone,4-chloro-2-cyano-N,N-dimethyl-5-p-tolylimidazole-1-sulfonamide (IKF-916,cyamidazosulfamid),3-5-dichloro-N-(3-chloro-1-ethyl-1-methyl-2-oxopropyl)-4-methylbenzamide(RH-7281, zoxamide),N-allyl-4,5,-dimethyl-2-trimethylsilylthiophene-3-carboxamide(MON65500),N-(1-cyano-1,2-dimethylpropyl)-2-(2,4-dichlorophenoxy)-propionamide(AC382042), N-(2-methoxy-5-pyridyl)-cyclopropane carboxamide,acibenzolar (CGA245704) (e.g. acibenzolar-S-methyl), alanycarb,aldimorph, anilazine, azaconazole, azoxystrobin, benalaxyl, benomyl,benthiavalicarb, biloxazol, bitertanol, bixafen, blasticidin S,boscalid, bromuconazole, bupirimate, captafol, captan, carbendazim,carbendazim chlorhydrate, carboxin, carpropamid, carvone, CGA41396,CGA41397, chinomethionate, chlorothalonil, chlorozolinate, clozylacon,copper containing compounds such as copper oxychloride, copperoxyquinolate, copper sulfate, copper tallate and Bordeaux mixture,cyclufenamid, cymoxanil, cyproconazole, cyprodinil, debacarb,di-2-pyridyl disulfide 1,1′-dioxide, dichlofluanid, diclomezine,dicloran, diethofencarb, difenoconazole, difenzoquat, diflumetorim,0,0-di-iso-propyl-S-benzyl thiophosphate, dimefluazole, dimetconazole,dimethomorph, dimethirimol, diniconazole, dinocap, dithianon, dodecyldimethyl ammonium chloride, dodemorph, dodine, doguadine, edifenphos,epoxiconazole, ethirimol,ethyl-(Z)-N-benzyl-N-([methyl(methyl-thioethylideneamino-oxycarbonyl)amino]thio)-β-alaninate,etridiazole, famoxadone, fenamidone (RPA407213), fenarimol,fenbuconazole, fenfuram, fenhexamid (KBR2738), fenpiclonil, fenpropidin,fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone,fluazinam, fludioxonil, flumetover, fluopyram, fluoxastrobin,fluoroimide, fluquinconazole, flusilazole, flutolanil, flutriafol,fluxapyroxad, folpet, fuberidazole, furalaxyl, furametpyr, guazatine,hexaconazole, hydroxyisoxazole, hymexazole, imazalil, imibenconazole,iminoctadine, iminoctadine triacetate, ipconazole, iprobenfos,iprodione, iprovalicarb (SZX0722), isopropanyl butyl carbamate,isoprothiolane, isopyrazam, kasugamycin, kresoxim-methyl, LY186054,LY211795, LY248908, mancozeb, mandipropamid, maneb, mefenoxam,metalaxyl, mepanipyrim, mepronil, metalaxyl, metconazole, metiram,metiram-zinc, metominostrobin, myclobutanil, neoasozin, nickeldimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace,organomercury compounds, oxadixyl, oxasulfuron, oxolinic acid,oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron,penflufen, penthiopyrad, phenazin oxide, phosetyl-A1, phosphorus acids,phthalide, picoxystrobin (ZA1963), polyoxinD, polyram, probenazole,prochloraz, procymidone, propamocarb, propiconazole, propineb, propionicacid, prothioconazole, pyrazophos, pyrifenox, pyrimethanil,pyraclostrobin, pyroquilon, pyroxyfur, pyrrolnitrin, quaternary ammoniumcompounds, quinomethionate, quinoxyfen, quintozene, sedaxane,sipconazole (F-155), sodium pentachlorophenate, spiroxamine,streptomycin, sulfur, tebuconazole, tecloftalam, tecnazene,tetraconazole, thiabendazole, thifluzamid,2-(thiocyanomethylthio)benzothiazole, thiophanate-methyl, thiram,timibenconazole, tolclofos-methyl, tolylfluanid, triadimefon,triadimenol, triazbutil, triazoxide, tricyclazole, tridemorph,trifloxystrobin (CGA279202), triforine, triflumizole, triticonazole,validamycin A, vapam, vinclozolin, zineb and ziram, a compound offormula (A), a compound of formula (B) and a compound of formula (C)

The compounds of formula (I) may be mixed with soil, peat or otherrooting media for the protection of plants against seed-borne,soil-borne or foliar fungal diseases.

Examples of suitable synergists for use in the compositions includepiperonyl butoxide, sesamex, safroxan and dodecyl imidazole.

Suitable herbicides and plant-growth regulators for inclusion in thecompositions will depend upon the intended target and the effectrequired.

An example of a rice selective herbicide which may be included ispropanil. An example of a plant growth regulator for use in cotton isPIX™.

Some mixtures may comprise active ingredients which have significantlydifferent physical, chemical or biological properties such that they donot easily lend themselves to the same conventional formulation type. Inthese circumstances other formulation types may be prepared. Forexample, where one active ingredient is a water insoluble solid and theother a water insoluble liquid, it may nevertheless be possible todisperse each active ingredient in the same continuous aqueous phase bydispersing the solid active ingredient as a suspension (using apreparation analogous to that of an SC) but dispersing the liquid activeingredient as an emulsion (using a preparation analogous to that of anEW). The resultant composition is a suspoemulsion (SE) formulation.

The following Examples illustrate, but do not limit, the invention.

PREPARATION EXAMPLES

The following abbreviations were used in this section: s=singlet;bs=broad singlet; d=doublet; dd=double doublet; dt=double triplet;t=triplet, tt=triple triplet, q=quartet, sept=septet; m=multiplet;Me=methyl; Et=ethyl; Pr=propyl; Bu=butyl; M.p.=melting point;RT=retention time, [M+H]⁺=molecular mass of the molecular cation,[M−H]⁻=molecular mass of the molecular anion.

The following LC-MS methods were used to characterize the compounds:

Method A

MS ZQ Mass Spectrometer from Waters (single quadrupole massspectrometer), ionization method: electrospray, polarity: positiveionization, capillary (kV) 3.00, cone (V) 30.00, source temperature (°C.) 100, desolvation temperature (° C.) 250, cone gas flow (L/Hr) 50,desolvation gas flow (L/Hr) 400, mass range: 150 to 1000 Da. LC HP 1100HPLC from Agilent: solvent degasser, quaternary pump, heated columncompartment and diode-array detector. Column: Phenomenex Gemini C18,length (mm) 30, internal diameter (mm) 3, particle size (μm) 3,temperature (° C.) 60, DAD wavelength range (nm): 200 to 500, solventgradient: A = 0.05% v/v formic acid in water and B = 0.04% v/v formicacid in acetonitrile/methanol (4:1). Time (min) A % B % Flow (ml/min)0.0 95 5.0 1.7 2.0 0.0 100 1.7 2.8 0.0 100 1.7 2.9 95 5.0 1.7

Method B

MS ZMD Mass Spectrometer from Waters (single quadrupole massspectrometer), ionization method: electrospray, polarity: positiveionization, capillary (kV) 3.00, cone (V) 30.00, extractor (V) 3.00,source temperature (° C.) 150, desolvation temperature (° C.) 320, conegas flow (L/Hr) 50, desolvation gas flow (L/Hr) 400, mass range: 150 to800 Da. LC Alliance 2795 LC HPLC from Waters: quaternary pump, heatedcolumn compartment and diode-array detector. Column: Waters Atlantisdc18, length (mm) 20, internal diameter (mm) 3, particle size (μm) 3,temperature (° C.) 40, DAD wavelength range (nm): 200 to 500, solventgradient: A = 0.1% v/v formic acid in water and B = 0.1% v/v formic acidin acetonitrile. Time (min) A % B % Flow (ml/min) 0.0 80 20 1.7 5.0 0.0100 1.7 5.6 0.0 100 1.7 6.0 80 20 1.7

Method C

MS ZQ Mass Spectrometer from Waters (single quadrupole massspectrometer), ionization method: electrospray, polarity: positiveionization, capillary (kV) 3.00, cone (V) 30.00, extractor (V) 3.00,source temperature (° C.) 100, desolvation temperature (° C.) 200, conegas flow (L/Hr) 200, desolvation gas flow (L/Hr) 250, mass range: 150 to800 Da. LC 1100er Series HPLC from Agilent: quaternary pump, heatedcolumn compartment and diode-array detector. Column: Waters Atlantisdc18, length (mm) 20, internal diameter (mm) 3, particle size (μm) 3,temperature (° C.) 40, DAD wavelength range (nm): 200 to 500, solventgradient: A = 0.1% v/v formic acid in water and B = 0.1% v/v formic acidin acetonitrile. Time (min) A % B % Flow (ml/min) 0.0 90 10 1.7 5.5 0.0100 1.7 5.8 0.0 100 1.7 5.9 90 10 1.7

Method D

MS ZMD Mass Spectrometer from Waters (single quadrupole massspectrometer), ionization method: electrospray, polarity: positiveionization, capillary (kV) 3.00, cone (V) 30.00, extractor (V) 3.00,source temperature (° C.) 150, desolvation temperature (° C.) 320, conegas flow (L/Hr) 50, desolvation gas flow (L/Hr) 400, mass range: 150 to800 Da. LC Alliance 2795 LC HPLC from Waters: quaternary pump, heatedcolumn compartment and diode-array detector. Column: Waters Atlantisdc18, length (mm) 20, internal diameter (mm) 3, particle size (μm) 3,temperature (° C.) 40, DAD wavelength range (nm): 200 to 500, solventgradient: A = 0.1% v/v formic acid in water and B = 0.1% v/v formic acidin acetonitrile. Time (min) A % B % Flow (ml/min) 0.0 80 20 1.7 2.5 0.0100 1.7 2.8 0.0 100 1.7 2.9 80 20 1.7

Method E

MS ZQ Mass Spectrometer from Waters (single quadrupole massspectrometer), ionization method: electrospray, polarity: positiveionization, capillary (kV) 3.00, cone (V) 30.00, extractor (V) 3.00,source temperature (° C.) 100, desolvation temperature (° C.) 200, conegas flow (L/Hr) 200, desolvation gas flow (L/Hr) 250, mass range: 150 to800 Da. LC 1100er Series HPLC from Agilent: quaternary pump, heatedcolumn compartment and diode-array detector. Column: Waters Atlantisdc18, length (mm) 20, internal diameter (mm) 3, particle size (μm) 3,temperature (° C.) 40, DAD wavelength range (nm): 200 to 500, solventgradient: A = 0.1% v/v formic acid in water and B = 0.1% v/v formic acidin acetonitrile. Time (min) A % B % Flow (ml/min) 0.0 80 20 1.7 2.5 0.0100 1.7 2.8 0.0 100 1.7 2.9 80 20 1.7

Example I1 Preparation of 4-bromo-3-methyl-benzylamine

To a solution of 4-bromo-3-methyl-benzonitrile (commercially available)(15 g) in diethyl ether (150 ml) under an argon atmosphere was added asolution of lithium aluminum hydride in diethyl ether (1M) (150 ml) atambient temperature. The reaction mixture was stirred at 40° C. for 2hours. Then the reaction mixture was cooled to 0° C. and quenched bysuccessive addition of water (10.5 ml), aqueous sodium hydroxide (20%w/w) (7.5 ml) and water (37.5 ml). The phases were separated. Theorganic phase was filtered through a plug of silica gel and the filtrateconcentrated to give 4-bromo-3-methyl-benzylamine (15.11 g) as a yellowoil. 1H-NMR (400 MHz, CDCl₃): 7.47 (d, 1H), 7.19 (s, 1H), 6.98 (d, 1H),3.80 (s, 2H), 2.39 (s, 3H) ppm.

Example I2 Preparation of N-(4-bromo-3-methyl-benzyl)-formamide

To a solution of 4-bromo-3-methyl-benzylamine (15.11 g) (Example ID inethyl formate (150 ml) was added triethylamine (1.5 ml) at ambienttemperature. The reaction mixture was stirred at reflux for 16 hours.The reaction mixture was concentrated and the residue was trituratedwith diisopropyl ether/heptane (1:1) (100 ml) to giveN-(4-bromo-3-methyl-benzyl)-formamide (14.04 g) as a white solid. 1H-NMR(400 MHz, CDCl₃): 8.28 (s, 1H), 7.49 (m, 1H), 7.16 (s, 1H), 6.97 (m,1H), 5.85 (s, 1H), 4.42 (m, 2H), 2.39 (s, 3H) ppm.

Example I3 Preparation of 1-bromo-4-isocyanomethyl-2-methyl-benzene

To a solution of N-(4-bromo-3-methyl-benzyl)-formamide (4.3 g) (ExampleI2) in dichloromethane (70 ml) was added a solution of phosphorusoxychloride (2.8 g) in dichloromethane (15 ml) at 0-5° C. The reactionmixture was stirred at ambient temperature for 16 hours. The reactionmixture was poured onto a mixture of ice and water (400 ml), and sodiumhydrogen carbonate (saturated) (100 ml) and ethyl acetate (250 ml) wereadded. The phases were separated and the organic phase was washed withbrine, dried over sodium sulfate and concentrated to give1-bromo-4-isocyanomethyl-2-methyl-benzene (4.52 g) as a brown oil.1H-NMR (400 MHz, CDCl₃): 7.54 (m, 1H), 7.22 (s, 1H), 7.03 (m, 1H), 4.57(s, 2H), 2.42 (s, 3H) ppm.

Example I4 Preparation of2-(4-bromo-3-methyl-phenyl)-4-(3,5-dichloro-phenyl)-4-trifluoromethyl-3,4-dihydro-2H-pyrrole

A mixture of 1,3-dichloro-5-(1-trifluoromethyl-vinyl)-benzene (8.03 g)(made as described in EP 1,731,512),1-bromo-4-isocyanomethyl-2-methyl-benzene (Example I3) (4.16 g) andcopper(I) oxide (0.13 g) in toluene (50 ml) was stirred at 110° C. for16 hours. The reaction mixture was concentrated and the residue purifiedby chromatography on silica gel (eluent: ethyl acetate/heptane) to give2-(4-bromo-3-methyl-phenyl)-4-(3,5-dichloro-phenyl)-4-trifluoromethyl-3,4-dihydro-2H-pyrrole(2.39 g). 1H-NMR (400 MHz, CDCl₃): 7.39-6.86 (m, 7H), 5.39-4.98 (m, 1H),3.24-2.77 (m, 1H), 2.35 (m, 3H), 2.32-2.09 (m, 1H) ppm.

Example I5 Preparation of4-[4-(3,5-dichloro-phenyl)-4-trifluoromethyl-3,4-dihydro-2H-pyrrol-2-yl]-2-methyl-benzoicacid ethyl ester

To a solution of2-(4-bromo-3-methyl-phenyl)-4-(3,5-dichloro-phenyl)-4-trifluoromethyl-3,4-dihydro-2H-pyrrole(Example I4) (7.0 g) in a mixture of ethanol (60 ml) anddimethylformamide (20 ml), was added dichloro1,1′-bis(diphenylphosphino)ferrocene palladium(II) dichloromethaneadduct (“Pd(dppf)Cl₂”) (0.8 g) and sodium acetate (1.4 g) at ambienttemperature. The reaction mixture was stirred in a pressure reactor inan atmosphere of carbon monoxide (6 bar) at 85° C. for 16 hours. Thereaction mixture was cooled to ambient temperature, the ethanol wasevaporated and aqueous sodium hydrogen carbonate (saturated) (200 ml)and ethyl acetate (250 ml) were added. The phases were separated and theorganic phase was dried over sodium sulfate and concentrated. Theresidue was purified by chromatography on silica gel (eluent: gradientof 0-4% v/v methanol in dichloromethane) to give4-[4-(3,5-dichloro-phenyl)-4-trifluoromethyl-3,4-dihydro-2H-pyrrol-2-yl]-2-methyl-benzoicacid ethyl ester (2.8 g). 1H-NMR (CDCl₃, 400 MHz): 8.04-7.06 (m, 7H),5.46-5.06 (m, 1H), 4.35 (m, 2H), 3.27-3.79 (m, 1H), 2.59 (m, 3H),2.38-2.10 (m, 1H), 1.39 (m, 3H) ppm.

Example I6 Preparation of4-[4-(3,5-dichloro-phenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrrol-2-yl]-2-methyl-benzoicacid

To a solution of4-[4-(3,5-dichloro-phenyl)-4-trifluoromethyl-3,4-dihydro-2H-pyrrol-2-yl]-2-methyl-benzoicacid ethyl ester (Example I5) (2.8 g) in ethanol (40 ml) was added asolution of sodium hydroxide (0.51 g) in water (15 ml). The reactionmixture was stirred at reflux for 1 hour. After cooling to ambienttemperature aqueous hydrochloric acid (1M) (20 ml), water (150 ml) andethyl acetate (200 ml) was added. The phases were separated and theorganic phase was washed with brine, dried over sodium sulfate andconcentrated. The residue was recrystallised from diisopropyl ether togive4-[4-(3,5-dichloro-phenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrrol-2-yl]-2-methyl-benzoicacid (2.02 g) as a white solid. 1H-NMR (d₆-DMSO, 400 MHz): 13.07 (s,1H), 7.91-7.58 (m, 6H), 4.85 (d, 1H), 4.44 (d, 1H), 3.92-3.35 (m, 2H),2.58 (s, 3H) ppm.

Example I7 Preparation of2-methyl-N-trimethylsilanylmethyl-terephthalamic acid methyl ester

To a solution of 2-methyl-terephthalic acid 1-methylester (preparationsee WO 2000/021920) (1.43 g) in dichloromethane (10 ml) was addedN-(−3-dimethylaminopropyl)-N′-ethylcarbodiimid hydrochloride (1.84 g),N,N-dimethylaminopyridine (0.41 g) and trimethylsilylmethylamine (1 ml).The reaction mixture was stirred at ambient temperature. for 2 hours.The reaction mixture was concentrated and the residue purified bychromatography on silica gel (eluent: ethyl acetate/heptanes 1:3) togive 2-methyl-N-trimethylsilanylmethyl-terephthalamic acid methyl ester(1.85 g). 1H-NMR (400 MHz, CDCl₃): 7.72 (d, 1H), 7.45 (s, 1H), 7.40 (d,1H), 5.85 (s, 1H), 3.78 (s, 3H), 2.84 (d, 2H), 2.49 (s, 3H), 0.00 (s,9H) ppm. 2-Methyl-N-trimethylsilanylmethyl-terephthalamic acidtert-butyl ester was obtained using a similar procedure. 1H-NMR (400MHz, CDCl₃): 7.82 (d, 1H), 7.48 (s, 1H), 7.39 (d, 1H), 5.70 (s, 1H),2.82 (d, 2H), 2.48 (s, 3H), 1.48 (s, 9H), 0.00 (s, 9H) ppm.

Example I8 Preparation of2-methyl-4-(trimethylsilanylmethyl-thiocarbamoyl)-benzoic acid methylester

To a solution of 2-methyl-N-trimethylsilanylmethyl-terephthalamic acidmethyl ester (Example I7) (1.83 g) in toluene (50 ml) was added2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide(Lawesson reagent) (2.65 g). The reaction mixture was stirred at ambienttemperature for 30 minutes and then at 110° C. for 1.5 hours. Thereaction mixture was concentrated and the residue purified bychromatography on silica gel (eluent: ethyl acetate/heptanes 1:5) togive 2-methyl-4-(trimethylsilanylmethyl-thiocarbamoyl)-benzoic acidmethyl ester (1.85 g). 1H-NMR (400 MHz, CDCl₃): 7.75-7.20 (m, 3H), 3.70(s, 3H), 3.35 (m, 2H), 2.45 (s, 3H), 0.00 (s, 9H) ppm.2-Methyl-4-(trimethylsilanylmethyl-thiocarbamoyl)-benzoic acidtert-butyl ester was obtained using a similar procedure. ¹H-NMR (400MHz, CDCl₃): 7.62 (d, 1H), 7.40 (s, br, 1H), 7.35 (s, 1H), 7.25 (d, 1H),3.35 (d, 2H), 2.40 (s, 3H), 1.40 (s, 9H), 0.00 (s, 9H) ppm.

Example I9 Preparation of2-methyl-4-(methylsulfanyl-trimethylsilanylmethylimino]-methyl)-benzoicacid methyl ester

To a solution of2-methyl-4-(trimethylsilanylmethyl-thiocarbamoyl)-benzoic acid methylester (Example I8) (200 mg) in acetonitrile (4 ml) was added potassiumcarbonate (140 mg) and methyl iodide (120 mg). The reaction mixture wasstirred at ambient temperature for 20 hours. Water and ethyl acetate wasadded to the reaction mixture. The phases were separated and the organicphase was washed with brine, dried over sodium sulfate and concentrated.The residue purified by chromatography on silica gel (eluent: ethylacetate/heptanes 1:5) to give2-methyl-4-(methylsulfanyl-trimethylsilanylmethylimino]-methyl)-benzoicacid methyl ester (124 mg). 1H-NMR (400 MHz, CDCl₃): 7.82-7.20 (m, 3H),3.80 (s, 3H), 3.50 (m, 2H), 2.50 (s, 3H), 1.92 (s, 3H), 0.00 (s, 9H)ppm.2-Methyl-4-{methylsulfanyl-RE)-trimethylsilanylmethylimino]-methyl}-benzoicacid tert-butyl ester was obtained using a similar procedure. 1H-NMR(400 MHz, CDCl₃): 7.62 (d, 1H), 7.23-7.20 (m, 2H), 3.03 (m, 2H), 2.48(s, 3H), 1.95 (s, 3H), 1.45 (s, 9H), 0.00 (s, 9H) ppm.

Example I10 Preparation of4-[4-(3,5-Bis-trifluoromethyl-phenyl)-4-trifluoromethyl-3,4-dihydro-2H-pyrrol-2-yl]-2-methyl-benzoicacid methyl ester

To a solution of2-methyl-4-(methylsulfanyl-trimethylsilanylmethylimino]-methyl)-benzoicacid methyl ester (Example I9) (135 mg) and1,3-bis-trifluoromethyl-5-(1-trifluoromethyl-vinyl)-benzene (see WO2007125984) (179 mg) in THF (5 ml) was added at 5° C. tetrabutylammoniumfluoride (TBAF) (0.11 ml, 1M in THF). The reaction mixture was stirredat ambient temperature for 5 hours. The reaction mixture was filteredover silica and concentrated. The residue was purified by preparativeHPLC to give4-[4-(3,5-bis-trifluoromethyl-phenyl)-4-trifluoromethyl-3,4-dihydro-2H-pyrrol-2-yl]-2-methyl-benzoicacid methyl ester (124 mg). ¹H-NMR (400 MHz, CDCl₃): 8.60-7.70 (m, 6H),5.03 (d, 1H), 4.52 (d, 1H), 3.98-3.90 (m, 4H), 3.55-3.40 (m, 1H), 2.68(s, 3H) ppm.2-Methyl-4-[4-(3,4,5-trichloro-phenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrrol-2-yl]-benzoicacid methyl ester was obtained using a similar procedure. ¹H-NMR (400MHz, CDCl₃): 8.0-7.42 (m, 5H), 4.90 (d, 1H), 4.45 (d, 1H), 3.93 (s, 3H),3.80 (d, 1H), 3.45 (d, 1H), 2.65 (s, 3H) ppm.

Example I11 Preparation of4-[4-(3,5-Bis-trifluoromethyl-phenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrrol-2-yl]-2-methyl-benzoicacid

To a solution of2-methyl-4-(methylsulfanyl-trimethylsilanylmethylimino]-methyl)-benzoicacid methyl ester (Example I10) (115 mg) in THF (4 ml) and water (2 ml)was added Lithium hydroxide monohydrate (24 mg). The reaction mixturewas stirred at 50° C. for 16 hours. The reaction mixture was cooled toambient temperature and diluted with water, acidified by addition ofaqueous hydrochloric acid (1M) and extracted twice with ethyl acetate.The combined organic phases were washed with brine, dried over sodiumsulfate and concentrated to give4-[4-(3,5-Bis-trifluoromethyl-phenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrrol-2-yl]-2-methyl-benzoicacid (109 mg). ¹H-NMR (400 MHz, CDCl₃): 8.15-7.72 (m, 6H), 5.05 (d, 1H),4.55 (d, 1H), 3.95 (d, 1H), 3.55 (d, 1H), 2.70 (s, 3H) ppm.2-Methyl-4-[4-(3,4,5-trichloro-phenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrrol-2-yl]-benzoicacid was obtained using a similar procedure. ¹H-NMR (400 MHz, CDCl₃):7.95-7.55 (m, 5H), 4.76 (d, 1H), 4.30 (d, 1H), 3.65 (d, 1H), 3.30 (d,1H), 2.55 (s, 3H) ppm.

Example I12 Preparation of4-Bromo-3-chloro-N-trimethylsilanylmethyl-benzamide

To a solution of 4-bromo-3-chloro-benzoic acid (commercially available)(5.0 g) in dichloromethane (30 ml) was addedN-(−3-dimethylaminopropyl)-N′-ethylcarbodiimid hydrochloride (5.29 g),N,N-dimethylaminopyridine (1.19 g) and trimethylsilylmethylamine (2.85ml). The reaction mixture was stirred at ambient temperature for 5hours. Water and dichloromethane was added to the reaction mixture. Thephases were separated and the organic phase was washed with brine, driedover sodium sulfate and filtered through silica gel. The reactionmixture was concentrated to give4-bromo-3-chloro-N-trimethylsilanylmethyl-benzamide (4.87 g). 1H-NMR(400 MHz, CDCl₃): 7.68 (d, 1H), 7.55 (s, 1H), 7.33 (d, 1H), 5.85 (s,1H), 2.84 (d, 2H), 0.00 (s, 9H) ppm.

Example I13 Preparation of4-Bromo-3-chloro-N-trimethylsilanylmethylthiobenzamide

To a solution of 4-bromo-3-chloro-N-trimethylsilanylmethyl-benzamide(Example I12) (4.6 g) in toluene (150 ml) was added2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide(Lawesson reagent) (5.8 g). The reaction mixture was stirred at ambienttemperature for 30 minutes and then at 110° C. for 1.5 hours. Thereaction mixture was concentrated and the residue purified bychromatography on silica gel (eluent: ethyl acetate/heptanes 1:5) togive 4-bromo-3-chloro-N-trimethylsilanylmethylthiobenzamide (4.64 g).1H-NMR (400 MHz, CDCl₃): 1H-NMR (400 MHz, CDCl₃): 7.60 (d, 1H), 7.45 (s,1H), 7.30 (s, 1H), 7.25 (d, 1H), 3.33 (d, 2H), 0.00 (s, 9H) ppm.

Example I14 Preparation of4-Bromo-3-chloro-N-trimethylsilanylmethyl-thiobenzimidic acid methylester

To a solution of 4-bromo-3-chloro-N-trimethylsilanylmethylthiobenzamide(Example I13) (4.43 g) in butanone (80 ml) was added potassium carbonate(2.73 g) and methyl iodide (1.02 ml). The reaction mixture was stirredat ambient temperature for 20 hours. The reaction mixture wasconcentrated and the residue purified by chromatography on silica gel(eluent: ethyl acetate/heptanes 1:5) to give of4-bromo-3-chloro-N-trimethylsilanylmethyl-thiobenzimidic acid methylester (2.56 g). 1H-NMR (400 MHz, CDCl₃): 7.55-7.15 (m, 3H), 3.55 (s,2H), 1.98 (s, 3H), 0.00 (s, 9H) ppm.

Example I15 Preparation of5-(4-Bromo-3-chloro-phenyl)-3-(3,5-dichloro-phenyl)-3-methyl-3,4-dihydro-2H-pyrrole

To a solution of4-bromo-3-chloro-N-trimethylsilanylmethyl-thiobenzimidic acid methylester (Example I14) (1.83 g) and1,3-dichloro-5-(1-trifluoromethyl-vinyl)-benzene (see WO 2007125984)(1.38 g) in THF (25 ml) was added at −5° C. tetrabutylammonium fluoridetrihydrate (TBAF) (0.41 g) dissolved in THF (15 ml). The reactionmixture was stirred at ambient temperature for 16 hours. The reactionmixture concentrated and the residue was purified by chromatography onsilica gel (eluent: ethyl acetate/heptanes 1:6) to give5-(4-bromo-3-chloro-phenyl)-3-(3,5-dichloro-phenyl)-3-methyl-3,4-dihydro-2H-pyrrole(2.50 g). ¹H-NMR (400 MHz, CDCl₃): 7.95-7.25 (m, 6H), 4.88 (d, 1H), 4.42(d, 1H), 3.75 (d, 1H), 3.40 (d, 1H) ppm.

Example I16 Preparation of2-Chloro-4-[4-(3,5-dichloro-phenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrrol-2-yl]-benzoicacid butyl ester

Cataxium A (68 mg) and palladium acetate (13 mg) were dissolved inbutanol (30 ml) under an argon atmosphere. Tetramethylene diamine (0.29ml) and5-(4-bromo-3-chloro-phenyl)-3-(3,5-dichloro-phenyl)-3-methyl-3,4-dihydro-2H-pyrrole(1.11 g) were added at ambient temperature. The reaction mixture wasstirred in a pressure reactor in an atmosphere of carbon monoxide (6bar) at 115° C. for 16 hours. The reaction mixture was cooled to ambienttemperature, filtered and ethyl acetate (250 ml) was added. The mixturewas washed with water (50 ml), brine (50 ml), dried over anhydroussodium sulphate, filtered over a small layer of silica and concentrated.The residue was purified by chromatography on silica gel (eluent: ethylacetate/heptanes 1:4) to give2-chloro-4-[4-(3,5-dichloro-phenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrrol-2-yl]-benzoicacid butyl ester (0.49 g). ¹H-NMR (400 MHz, CDCl₃): 7.95-7.25 (m, 6H),4.92 (d, 1H), 4.45 (d, 1H), 4.37 (t, 2H), 3.78 (d, 1H), 3.45 (d, 1H),1.75 (m, 2H), 1.50 (m, 2H), 0.95 (t, 3H) ppm.

Example I17 Preparation of2-Chloro-4-[4-(3,5-dichloro-phenyl)-4-methyl-4,5-dihydro-3H-pyrrol-2-yl]-benzoicacid

To a solution of2-chloro-4-[4-(3,5-dichloro-phenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrrol-2-yl]-benzoicacid butyl ester (Example I16) (0.48 g) in THF (16 ml) and water (8 ml)was added lithium hydroxide monohydrate (103 mg). The reaction mixturewas stirred at 50° C. for 20 hours. The reaction mixture was cooled toambient temperature and diluted with water, acidified by addition ofaqueous hydrochloric acid (1M) and extracted twice with ethyl acetate.The combined organic phases were washed with brine, dried over sodiumsulfate and concentrated to give2-chloro-4-[4-(3,5-dichloro-phenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrrol-2-yl]-benzoicacid (459 mg). ¹H-NMR (400 MHz, CDCl₃): 8.15-7.40 (m, 6H), 4.95 (d, 1H),4.30 (d, 1H), 3.85 (d, 1H), 3.35 (d, 1H) ppm.

Example I18 Preparation of2-Methyl-4-{methylsulfanyl-[(Z)-trimethylsilanylmethylimino]methyl}-benzoic acid

To a solution of2-methyl-4-{methylsulfanyl-[(E)-trimethylsilanylmethylimino]-methyl}-benzoicacid tert-butyl ester (see Example I9) (118 mg) in dichloromethane (15ml) was added trifluoroacetic acid (0.22 ml). The reaction mixture wasstirred at ambient temperature for 20 hours. Further trifluoroaceticacid (0.11 ml) was added and the mixture was stirred for another 3 hoursat ambient temperature. Water was added and the mixture was extractedtwice with dichloromethane. The combined organic phases were washed withbrine, dried over sodium sulfate and concentrated to give2-methyl-4-{methylsulfanyl-[(Z)-trimethylsilanylmethylimino]methyl}-benzoic acid which was used without furtherpurification in the subsequent step.

LC-MS (Method A): RT (min): 1.32; [M+H]⁺:296

Example I19 Preparation of3-Methyl-4-(thietan-3-ylcarbamoyl)-N-trimethylsilanylmethyl-thiobenzimidicacid methyl ester

To a solution of 2-methyl-4-{methylsulfanyl-[(Z)-trimethylsilanylmethylimino]methyl}-benzoic acid (Example I18) (107 mg) indichloromethane (6 ml) was added thietan-3-ylamine (88 mg), Hünigs base(0.248 ml) and 2-bromo-1-ethyl-pyridinium tetrafluoroborate (169 mg).The reaction mixture was stirred at ambient temperature for 2 hours.Water was added and the mixture was extracted twice withdichloromethane. The combined organic phases were washed with brine,dried over sodium sulfate and concentrated. The residue was purified bychromatography on silica gel (eluent: ethyl acetate/heptanes 1:3) togive3-methyl-4-(thietan-3-ylcarbamoyl)-N-trimethylsilanylmethyl-thiobenzimidicacid methyl ester (16 mg). 1H-NMR (400 MHz, CDCl₃): 7.40-7.20 (m, 3H),6.20 (d, 1H); 5.30 (m, 1H), 3.55 (s, 2H), 3.35 (m, 2H), 3.25 (m, 2H),2.35 (s, 3H), 1.95 (s, 3H), 0.00 (s, 9H) ppm.

LC-MS (Methode A): RT (min): 1.33; [M+H]⁺:367

Example I20 Preparation of4-[4-(3,5-Dichloro-phenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrrol-2-yl]-2-methyl-N-thietan-3-yl-benzamide

To a solution of3-methyl-4-(thietan-3-ylcarbamoyl)-N-trimethylsilanylmethyl-thiobenzimidicacid methyl ester (Example I19) (16 mg) and1,3-dichloro-5-(1-trifluoromethyl-vinyl)-benzene (see WO 2007/125984)(12 mg) in THF (2 ml) was added at −5° C. tetrabutylammonium fluoridetrihydrate (TBAF) (0.41 g) dissolved in THF (1.5 ml). The reactionmixture was stirred at ambient temperature for 16 hours. Water was addedand the mixture was extracted twice with ethyl acetate. The combinedorganic phases were washed with brine, dried over sodium sulfate andconcentrated. The residue was purified by chromatography on silica gel(eluent: ethyl acetate/heptanes 1:2) to give4-[4-(3,5-dichloro-phenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrrol-2-yl]-2-methyl-N-thietan-3-yl-benzamide(20 mg). ¹H-NMR (400 MHz, CDCl₃): 7.75-7.25 (m, 6H), 6.30 (s, 1H), 5.45(m, 1H), 4.90 (d, 1H), 4.45 (d, 1H), 3.82 (d, 1H), 3.55-3.38 (m, 5H),2.48 (s, 3H) ppm.

Example I21 Preparation of4-[3-(3,5-Dichloro-phenyl)-4,4,4-trifluoro-3-nitromethyl-butyryl]-2-methyl-N-thietan-3-yl-benzamide

To a solution of4-[(Z)-3-(3,5-dichloro-phenyl)-4,4,4-trifluoro-but-2-enoyl]-2-methyl-N-thietan-3-yl-benzamide(general preparation described in WO 2009/080250) (100 mg) in DMF (1 ml)nitromethane (0.011 ml) and 1M sodium hydroxide (0.211 ml) was added atambient temperature. The reaction mixture was stirred at ambienttemperature for 1 hour. Water was added and the mixture was extractedtwice with ethyl acetate. The combined organic phases were washed withbrine, dried over sodium sulfate and concentrated. The residue waspurified by prep. HPLC to give4-[3-(3,5-dichloro-phenyl)-4,4,4-trifluoro-3-nitromethyl-butyryl]-2-methyl-N-thietan-3-yl-benzamide(78 mg). ¹H-NMR (400 MHz, CDCl₃): 7.85-7.20 (m, 6H), 6.25 (d, 1H), 5.62(d, 1H), 5.45 (m, 2H), 4.15 (d, 1H), 4.00 (d, 1H), 3.58-3.38 (m, 4H),2.55 (s, 3H) ppm.

Example I22 Preparation of4-[4-(3,5-Dichloro-phenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrrol-2-yl]-2-methyl-N-thietan-3-yl-benzamide

To a solution of4-[3-(3,5-dichloro-phenyl)-4,4,4-trifluoro-3-nitromethyl-butyryl]-2-methyl-N-thietan-3-yl-benzamide(Example I21) (78 mg) in DMF (1.5 ml) zinc powder (48 mg) was added atambient temperature. The reaction mixture was heated to 80° C. andconcentrated hydrochloric acid (0.3 ml) was added drop-wise. Thereaction mixture was stirred at 80° C. for 4 hours. Water was added andthe mixture was extracted twice with ethyl acetate. The combined organicphases were washed with brine, dried over sodium sulfate andconcentrated. The residue was purified by prep. HPLC to give4-[4-(3,5-dichloro-phenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrrol-2-yl]-2-methyl-N-thietan-3-yl-benzamide(12 mg). ¹H-NMR (400 MHz, CDCl₃): 7.75-7.25 (m, 6H), 6.35 (s, 1H), 5.45(m, 1H), 4.90 (d, 1H), 4.45 (d, 1H), 3.82 (d, 1H), 3.55-3.38 (m, 5H),2.48 (s, 3H) ppm.

Example P1 Method for Preparing the Compounds of the Invention from aCarboxylic Acid

To a solution of the appropriate carboxylic acid (30 μmol), for example4-[4-(3,5-dichloro-phenyl)-4-trifluoromethyl-4,5-dihydro-3H-pyrrol-2-yl]-2-methyl-benzoicacid (Example I6) in the case of Compound No. A1 of Table A, indimethylacetamide (0.4 ml) was added successively a solution of an amineof formula HNR¹R² (36 μmol), for example 1,1-dioxo-thietan-3-ylamine(preparation described in, for example, WO 2007/080131) in the case ofCompound No. A1 of Table A, in dimethylacetamide (0.145 ml),diisopropylethylamine (Hunig's Base) (0.02 ml, 100 μmol), and a solutionof bis(2-oxo-3-oxazolidinyl)phosphonic chloride (“BOP-Cl”) (15.3 mg) indimethylacetamide (0.2 ml). The reaction mixture was stirred at 100° C.for 16 hours. Then the reaction mixture was diluted with acetonitrile(0.6 ml) and a sample was used for LC-MS analysis. The remaining mixturewas further diluted with acetonitrile/dimethylformamide (4:1) (0.8 ml)and purified by HPLC. This method was used to prepare a number ofcompounds (Compound Nos. A1 to A4 of Table A) in parallel. CompoundsNos. A5 to A10, B1 to B4 and C1 to C were obtained using a similarprocedure.

TABLE A Table A provides compounds of formula (Ia) where G is oxygen, R³is trifluoromethyl, R⁴ is 3,5-dichloro-phenyl-, R⁵ is methyl, and R¹ andR² have the values listed in the table below. (Ia)

Compound LC-MS No. R¹ R² RT (min) [M + H]⁺ method A1 H1,1-dioxo-thietan-3-yl 3.04 519.0 C A2 H 3-methyl-thietan-3-yl 3.59501.0 C A3 H 1-oxo-thietan-3-yl- 2.82 503.0 C A4 H thietan-3-yl- 3.40487.0 C A5 H 1-oxo-cyclobutan-3-yl 1.97 483.0 A A6 H cyclobutanoneO-methyl-oxime-3-yl 2.04 512.0 A A7 H cyclobutanone O-benzyl-oxime-3-yl2.21 588.0 A A8 H thietan-2-yl-methyl- 2.04 501.0 A A9 H1-oxo-thietan-2-yl-methyl- 1.87 517.0 A A10 H1,1-dioxo-thietan-2-yl-methyl- 1.90 533 A

TABLE B Table B provides compounds of formula (Ia) where G is oxygen, R¹is Hydrogen, R⁵ is methyl, R³ is trifluoromethyl, and R² and R⁴ have thevalues listed in the table below. (Ia)

Compound LC-MS No. R² R⁴ RT (min) [M + H]⁺ method B1 thietan-3-yl-3,5-Bis trifluoromethyl-phenyl- 2.12 555.0 A B2 1,1-dioxo-thietan-3-yl-3,5-Bis trifluoromethyl-phenyl- 2.00 587.0 A B3 thietan-3-yl-3,4,5-Trichloro-phenyl- 2.16 523.0 A B4 1,1-dioxo-thietan-3-yl-3,4,5-Trichloro-phenyl- 2.03 555.0 A B5 1-oxo-thietan-3-yl-3,4,5-Trichloro-phenyl- 1.94 539.0 A B6 1-oxo-thietan-3-yl- 3,5-Bistrifluoromethyl-phenyl- 1.91 571.0 A

TABLE C Table C provides compounds of formula (Ia) where G is oxygen, R¹is Hydrogen, R⁴ is 3,5- dichloro-phenyl-, and R², R³ and R⁵ have thevalues listed in the table below. (Ia)

Compound LC-MS No. R² R³ R⁵ RT (min) [M + H]⁺ method C1 thietan-3-yl-CF₃— Cl— 2.06 509.0 A C2 1,1-dioxo-thietan-3-yl- CF₃— Cl— 1.97 541.0 AC3 1-oxo-thietan-3-yl- CF₃— Cl— 1.88 525.0 A

TABLE D Table D provides compounds of formula (Ib) where G is oxygen, R³is trifluoromethyl, R⁴ is 3,5-dichloro-phenyl- and R¹ and R² have thevalues listed in the table below. (Ib)

Compound LC-MS No. R¹ R² RT (min) [M + H]⁺ method D1 H -thietan-3-yl-2.09 523.0 A D2 H 1-oxo-thietan-3-yl- 1.93 539.0 A D3 H1,1-dioxo-thietan-3-yl- 1.97 555.0 A

BIOLOGICAL EXAMPLES

This Example illustrates the insecticidal and acaricidal properties ofcompounds of formula (I). The tests were performed as follows:

Spodoptera littoralis (Egyptian Cotton Leafworm):

Cotton leaf discs were placed on agar in a 24-well microtiter plate andsprayed with test solutions at an application rate of 200 ppm. Afterdrying, the leaf discs were infested with 5 L1 larvae. The samples werechecked for mortality, feeding behavior, and growth regulation 3 daysafter treatment (DAT).

The following compound gave at least 80% control of Spodopteralittoralis: A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, B1, B2, B3, B4, B5,B6, C1, C2, C3, D1, D2, D3

Heliothis virescens (Tobacco Budworm):

Eggs (0-24 h old) were placed in 24-well microtiter plate on artificialdiet and treated with test solutions at an application rate of 200 ppm(concentration in well 18 ppm) by pipetting.

After an incubation period of 4 days, samples were checked for eggmortality, larval mortality, and growth regulation.

The following compound gave at least 80% control of Heliothis virescens:A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, B1, B2, B3, B4, B5, B6, C1, C2,C3, D1, D2, D3.

Plutella xylostella (Diamond Back Moth):

24-well microtiter plate (MTP) with artificial diet was treated withtest solutions at an application rate of 200 ppm (concentration in well18 ppm) by pipetting. After drying, the MTP's were infested with L2larvae (7-12 per well). After an incubation period of 6 days, sampleswere checked for larval mortality and growth regulation.

The following compound gave at least 80% control of Plutella xylostella:A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, B1, B2, B3, B4, B5, B6, C1, C2,C3, D1, D2, D3.

Diabrotica balteata (Corn Root Worm):

A 24-well microtiter plate (MTP) with artificial diet was treated withtest solutions at an application rate of 200 ppm (concentration in well18 ppm) by pipetting. After drying, the MTP's were infested with L2larvae (6-10 per well). After an incubation period of 5 days, sampleswere checked for larval mortality and growth regulation.

The following compound gave at least 80% control of Diabrotica balteata:A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, B1, B2, B3, B4, B5, B6, C1, C2,C3, D1, D2, D3.

Thrips tabaci (Onion Thrips):

Sunflower leaf discs were placed on agar in a 24-well microtiter plateand sprayed with test solutions at an application rate of 200 ppm. Afterdrying, the leaf discs were infested with an aphid population of mixedages. After an incubation period of 7 days, samples were checked formortality.

The following compounds gave at least 80% control of Thrips tabaci: A1,A2, A3, A4, A5, A6, A7, A8, A9, A10, B1, B2, B3, B4, B5, B6, C1, C2, C3,D1, D2, D3.

Tetranychus urticae (Two-Spotted Spider Mite):

Bean leaf discs on agar in 24-well microtiter plates were sprayed withtest solutions at an application rate of 200 ppm. After drying, the leafdiscs are infested with mite populations of mixed ages. 8 days later,discs are checked for egg mortality, larval mortality, and adultmortality.

The following compound gave at least 80% control of Tetranychus urticae:A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, B1, B2, B3, B4, B5, B6, C1, C2,C3, D1, D2, D3.

1. A compound of formula (I)

where A¹, A², A³ and A⁴ are independently of each other C—H, C—R⁵ ornitrogen; G is oxygen or sulfur; R¹ is hydrogen, C₁-C₈alkyl,C₁-C₈alkoxy-, C₁-C₈alkylcarbonyl- or C₁-C₈alkoxycarbonyl-; R² is a groupof formula (II)

where L is a single bond or C₁-C₆alkylene; and Y¹, Y² and Y³ areindependently of another CR⁸R⁹, C═O, C═N—OR¹⁰, N—R¹⁰, S, SO, SO₂,S═N—R¹⁰ or SO═N—R¹⁰, provided that at least one of Y¹, Y² or Y³ is notCR⁸R⁹, C═O or C═N—OR¹⁰; R³ is C₁-C₈haloalkyl; R⁴ is phenyl substitutedby one to three R⁷; each R⁵ is independently halogen, cyano, nitro,C₁-C₈alkyl, C₁-C₈haloalkyl, C₁-C₈alkenyl, C₁-C₈haloalkenyl,C₁-C₈alkynyl, C₁-C₈haloalkynyl, C₃-C₁₀cycloalkyl, C₁-C₈alkoxy-,C₁-C₈haloalkoxy-, C₁-C₈alkylthio-, C₁-C₈haloalkylthio-,C₁-C₈alkylsulfinyl-, C₁-C₈haloalkylsulfinyl-, C₁-C₈alkylsulfonyl- orC₁-C₈haloalkylsulfonyl-, or two R⁵ on adjacent carbon atoms togetherform a —CH═CH—CH═CH— bridge; R⁶ is hydrogen or C₁-C₈alkyl; each R⁷ isindependently bromo, chloro, fluoro, cyano, methyl, trifluoromethyl,methoxy or trifluoromethoxy; each R⁸ and R⁹ is independently hydrogen,halogen, C₁-C₈alkyl or C₁-C₈haloalkyl; each R¹⁰ is independentlyhydrogen, cyano, C₁-C₈alkyl, C₁-C₈haloalkyl, C₁-C₈alkylcarbonyl-,C₁-C₈haloalkylcarbonyl-, C₁-C₈alkoxycarbonyl-, C₁-C₈haloalkoxycarbonyl-,C₁-C₈alkylsulfonyl-, C₁-C₈haloalkylsulfonyl-, aryl-C₁-C₄alkylene- oraryl-C₁-C₄alkylene- where the aryl moiety is substituted by one to threeR¹², or heteroaryl-C₁-C₄alkylene- or heteroaryl-C₁-C₄alkylene- where theheteroaryl moiety is substituted by one to three R¹²; each R¹² isindependently halogen, cyano, nitro, C₁-C₈alkyl, C₁-C₈haloalkyl,C₁-C₈alkoxy-, C₁-C₈haloalkoxy- or C₁-C₈alkoxycarbonyl-; or a salt orN-oxide thereof.
 2. A compound according to claim 1, wherein A¹ is C—R⁵,A² is C—H, A³ is C—H or nitrogen and A⁴ is C—H or nitrogen.
 3. Acompound according to claim 1, wherein G is oxygen.
 4. A compoundaccording to claim 1, wherein R¹ is hydrogen, methyl, ethyl,methylcarbonyl-, or methoxycarbonyl-.
 5. A compound according to claim1, wherein R² is a group of formula (IIc)

where R¹³ is C₁-C₈alkyl, m is 0, 1, 2, 3, 4, or 5, and Y² is S, SO, SO₂,S═N—R¹⁰, SO═N—R¹⁰ or C═N—OR¹⁰.
 6. A compound according to claim 1,wherein R³ is chlorodifluoromethyl or trifluoromethyl.
 7. A compoundaccording to claim 1, wherein R⁷ is bromo, chloro, fluoro, ortrifluoromethyl.
 8. A compound according to claim 1, wherein A¹, A², A³and A⁴ are independently of each other C—H or C—R⁵; G is oxygen; R¹ ishydrogen, methyl or ethyl; R² is a group of formula (IIb)

where L is a single bond, methylene ethylene or propylene; one of Y¹ andY² is S, SO, SO₂, S═N—R¹⁰, SO═N—R¹⁰ or C═N—OR¹⁰ and the other is CH₂; R³is chlorodifluoromethyl or trifluoromethyl; R⁴ is 3,5-dibromo-phenyl-,3,5-dichloro-phenyl-, 3,5-bis-(trifluoromethyl)-phenyl-,3,4-dichloro-phenyl-, 3,4,5-trichloro-phenyl- or3-trifluoromethyl-phenyl-; each R⁵ is independently bromo, chloro,fluoro, methyl, trifluoromethyl or vinyl, or two R⁵ on adjacent carbonatoms together form a —CH═CH—CH═CH— bridge; each R¹⁰ is independentlymethyl or hydrogen; R¹³ is hydrogen or C₁-C₈alkyl.
 9. A compoundaccording to claim 1, wherein A¹, A², A³ and A⁴ are independently ofeach other C—H or C—R⁵; G is oxygen; R¹ is hydrogen; R² is a group offormula (IIc)

where m is 0, 1, 2, 3, 4, or 5, and Y² is S, SO, SO₂, or C═N—OR¹⁰; R³ ischlorodifluoromethyl or trifluoromethyl; R⁴ is 3,5-dibromo-phenyl-,3,5-dichloro-phenyl-, 3,5-bis-(trifluoromethyl)-phenyl-,3,4-dichloro-phenyl-, 3,4,5-trichloro-phenyl- or3-trifluoromethyl-phenyl-; each R⁵ is independently bromo, chloro,fluoro, methyl, trifluoromethyl or vinyl, or two R⁵ on adjacent carbonatoms together form a —CH═CH—CH═CH— bridge; each R¹⁰ is independentlymethyl or hydrogen; R¹³ is methyl.
 10. A compound of formula (IA)

wherein A¹, A², A³, A⁴, R¹, R², R³ and R⁴ are as defined for a compoundof formula (I) in claim 1; G is oxygen; and R is C₁-C₆alkoxy; or acompound of formula (VA)

wherein A¹, A², A³, A⁴, R³ and R⁴ are as defined for a compound offormula (I) in claim 1; R is C₁-C₆alkoxy; and X^(A) is a halogen atom;or a compound of formula (XIA)

wherein A¹, A², A³, A⁴, R³ and R⁴ are as defined for a compound offormula (I) in claim 1; each R is independently C₁-C₆alkoxy; G isoxygen; and X^(A) is a halogen atom; or a compound of formula (XVII)

wherein A¹, A², A³, A⁴, R¹ and R² are as defined for a compound offormula (I) in claim 1; R^(1′), R^(2′) and R^(3′) are each independentlyC₁-C₈ alkyl, C₁-C₈ haloalkyl, phenyl or phenyl optionally substitutedwith one to five groups independently selected from halogen and C₁-C₈alkyl; and R^(4′) is C₁-C₈ alkyl or C₁-C₈ haloalkyl; or a compound offormula (XX)

wherein A¹, A², A³, A⁴, R¹, R², R³ and R⁴ are as defined for a compoundof formula (I) in claim 1; or a compound of formula (XXIV)

wherein A¹, A², A³, A⁴, R³ and R⁴ are as defined for a compound offormula (I) in claim 1; and X^(A) is a halogen atom; or a compound offormula (XXVI)

wherein A¹, A², A³, A⁴, R¹, R², R³ and R⁴ are as defined for a compoundof formula (I) in claim 1; or a compound of formula (XXVII)

wherein A¹, A², A³, A⁴, R³ and R⁴ are as defined for a compound offormula (I) in claim 1; and X^(A) is a halogen atom.
 11. A method ofcontrolling insects, acarines, nematodes or molluscs which comprisesapplying to a pest, to a locus of a pest, or to a plant susceptible toattack by a pest an insecticidally, acaricidally, nematicidally ormolluscicidally effective amount of a compound of formula (I) as definedin claim
 19. 12. An insecticidal, acaricidal, nematicidal ormolluscicidal composition comprising an insecticidally, acaricidally,nematicidally or molluscicidally effective amount of a compound offormula (I) as defined in claim
 1. 13. An insecticidal, acaricidal,nematicidal or molluscicidal composition according to claim 12comprising an additional compound having biological activity.
 14. Amethod of treatment of insect pests in or on animals, comprisingadministering an effective amount of a compound as defined in claim 1,or a composition comprising said compound, to an animal.
 15. A compoundaccording to claim 1, or a composition comprising said compound, for usein treatment of insect pests in or on animals.